WO2003002583A2 - Metallocenes and catalyst compositions derived therefrom - Google Patents

Metallocenes and catalyst compositions derived therefrom Download PDF

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Publication number
WO2003002583A2
WO2003002583A2 PCT/US2002/018718 US0218718W WO03002583A2 WO 2003002583 A2 WO2003002583 A2 WO 2003002583A2 US 0218718 W US0218718 W US 0218718W WO 03002583 A2 WO03002583 A2 WO 03002583A2
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Prior art keywords
indenyl
groups
butyl
zirconium
hafnium
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PCT/US2002/018718
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French (fr)
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WO2003002583A3 (en
Inventor
James R. Hart
William T. Haygood
Terry J. Burkhardt
Robert T. Li
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Exxonmobil Chemical Patents Inc.
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Priority claimed from US09/896,494 external-priority patent/US6870016B1/en
Priority claimed from US09/896,496 external-priority patent/US7122498B2/en
Application filed by Exxonmobil Chemical Patents Inc. filed Critical Exxonmobil Chemical Patents Inc.
Priority to EP02756172.9A priority Critical patent/EP1421090B1/en
Priority to JP2003508964A priority patent/JP2005522406A/en
Publication of WO2003002583A2 publication Critical patent/WO2003002583A2/en
Publication of WO2003002583A3 publication Critical patent/WO2003002583A3/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes

Definitions

  • This invention relates to metallocene compounds and their use in the preparation of catalyst compositions for olefin polymerization, particularly propylene homo- and copolymerization.
  • the present invention also relates to polymerisation processes using such catalyst compositions and polymer compositions obtainable by these processes.
  • metallocene compositions in olefin polymerization is well known. Metallocenes containing substituted, bridged indenyl derivatives are noted for their ability to produce isotactic propylene polymers having high isotacticity and narrow molecular weight distribution. Considerable effort has been made toward obtaining metallocene produced propylene polymers having ever-higher molecular weight and melting point and, thus, ever better strength (impact) properties, while maintaining suitable catalyst activity.
  • WO 98/40419 and WO 99/42497 both describe certain supported catalyst systems for producing propylene polymers having high melting point.
  • Metallocene compositions and their activators are often combined with a support material in order to obtain a catalyst system that is less likely to cause reactor fouling.
  • supported metallocene catalyst systems tend to result in a polymer having lower melting point than would otherwise be obtained if the metallocene were not supported.
  • metallocenes which not only afford propylene homopolymers having high melting points of (i.e., high stereotacticity), but also elastomeric copolymers having the high molecular weights required for the production of, e.g., impact copolymers, thereby making possible the production of satisfactory in situ blends of, e.g., propylene homopolymer and ethylene-propylene rubbers (EPR's) with a single catalyst composition in a single reactor or in a series of two or more reactors.
  • EPR's ethylene-propylene rubbers
  • the present inventors have found metallocene compounds which in combination with a cocatalyst (activator) make both propylene homopolymers having high melting points and elastomeric copolymers that are suitable for the production of impact copolymers in combination with these propylene homopolymers.
  • the present invention relates to novel metallocene compounds capable of providing propylene homo- and copolymers having high melting point and high molecular weight.
  • the present invention further relates to metallocene catalyst compositions comprising one or more of these compounds and one or more activators or cocatalysts, and optionally, support material, and to the use of such catalyst compositions in polymerization, in particular propylene polymerization.
  • the present invention provides metallocene compounds represented by formula (I):
  • M 1 is selected from titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten;
  • R 1 and R 2 are selected from hydrogen, halogen, hydroxy, C ⁇ -C ⁇ 0 alkyl groups, C ⁇ -
  • R and R are joined together to form a C 4 -C 0 alkanediyl group or a conjugated diene ligand which is coordinated to M 1 in a metallacyclopentene fashion; or R 1 and R 2 represent a conjugated diene, optionally substituted with one or more groups independently selected from hydrocarbyl, trihydrocarbylsilyl and trihydrocarbylsilylhydrocarbyl groups, said diene having a total of up to 40 atoms not counting hydrogen and forming a ⁇ complex with M 1 ;
  • R 3 is selected from hydrogen, halogen, Ci-Cio alkyl groups, C 6 -C ⁇ 4 aryl groups, C 2 -C )0 alkenyl groups, C -C 40 arylalkyl groups, C 7 -C 40 alkylaryl groups, C 8 -C 40 arylalkenyl groups, and -NR' 2 , -SR', -OR', -SiR * 3 , -OSiR' 3 and -PR' 2 radicals wherein each R' is independently selected from halogen, Ci-Cio alkyl groups and C 6 -C ⁇ 4 aryl groups; provided that if R 1 and R 2 both are halogen and R 13 is dimethylsilanediyl, R 3 is different from methyl and ethyl;
  • R 4 , R 5 , R 6 and R 7 are each independently selected from hydrogen, halogen, C ⁇ -C ⁇ 0 alkyl groups, C -C ⁇ 4 aryl groups, C 2 -C ⁇ 0 alkenyl groups, C -C 40 arylalkyl groups, C 7 -C 40 alkylaryl groups, C 8 -C 40 arylalkenyl groups, and -NR' 2 , -SR', -OR', -SiR' 3 , -
  • OSiR' 3 and -PR' 2 radicals wherein each R' is independently selected from halogen, C 1 -C1 0 alkyl groups and C 6 -C ⁇ 4 aryl groups; or two or more adjacent radicals R 5 , R 6 and R 7 together with the atoms connecting them may form one or more rings;
  • R 8 , R 9 , R 10 and R 11 are each independently as defined for R 4 , R 5 , R 6 and R 7 , provided that two or more adjacent radicals R 8 ' R 9 , R 10 and R 11 together with the atoms connecting them may form one or more rings;
  • R 12 is selected from halogen, CpCio alkyl groups, C 6 -C 14 aryl groups, C2-C1 0 alkenyl groups, C 7 -C 40 arylalkyl groups, C -C 40 alkylaryl groups, C 8 -C 40 arylalkenyl groups, and -NR' 2 , -SR', -OR', -SiR' 3 , -OSiR' 3 and -PR' 2 radicals wherein each R' is independently selected from halogen, C 1 -C 10 alkyl groups and
  • R 13 is selected from
  • R 14 , R 15 and R 1 are each independently selected from hydrogen, halogen, C ⁇ -C 20 alkyl groups, C 6 -C 30 aryl groups, C ⁇ -C 20 alkoxy groups, C 2 -C 20 alkenyl groups, C 7 -C 4 o arylalkyl groups, C -C 0 arylalkenyl groups and C 7 -C 0 alkylaryl groups, or R 14 and R 15 , together with the atom(s) connecting them, form a ring; and M 3 is selected from carbon, silicon, germanium and tin; or R is represented by the formula
  • R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 and R 24 are each independently selected from hydrogen, halogen, hydroxy, C ⁇ -C ⁇ 0 alkyl groups, C ⁇ -C ⁇ 0 alkoxy groups, C 6 -C ⁇ 4 aryl groups, C 6 -C ⁇ 4 aryloxy groups, C 2 -C ⁇ o alkenyl groups, C 7 -C 40 arylalkyl groups, C 7 -C 40 alkylaryl groups and C 8 -C 40 arylalkenyl groups; or two or more adjacent radicals R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 and R 24 , including R 20 and R 21 , together with the atoms connecting them, form one or more rings; and
  • M represents one or more carbon atoms, or a silicon, germanium or tin atom.
  • M 1 is selected from titanium, zirconium and hafnium and R and R are selected from chlorine, C ⁇ -C 6 alkyl groups, C 6 -C] 0 aryl groups, C 7 -C ⁇ 2 arylalkyl groups and C 7 -C ⁇ 2 alkylaryl groups.
  • R may be a C 3 -C 6 alkyl group such as, e.g., a branched C 3 -C 4 alkyl group and, in particular, an isopropyl group, or may be a phenyl group.
  • At least one of R and R and most preferred both of them, represent hydrogen atoms. - 1 ⁇
  • M may be selected from carbon and silicon
  • R 14 , R 15 and R 16 may independently be selected from C]-C 4 alkyl groups and C 6 - Cio aryl groups.
  • R 13 is represented by the formula
  • R , 1"7, R , 18 , R , 19 , R ,20 , R , R ,22 , W »23 i and R 24 4 may each be hydrogen, with M representing a silicon atom.
  • R 12 may be selected from C ⁇ -C 6 alkyl groups and C 6 -C ⁇ 0 aryl groups, a preferred meaning being phenyl.
  • R 11 is different from hydrogen and may represent, e.g., a C ⁇ -C 4 alkyl group.
  • Particularly preferred compounds of the above formula include those wherein R and R are selected from chlorine, methyl, neopentyl and benzyl, R is selected from C 3 -C 4 alkyl groups, each of R 4 and R 8 is hydrogen, and R 12 is selected from C ⁇ -C 4 alkyl groups and C 6 -C ⁇ 0 aryl groups; wherein R is selected from branched C 3 -C alkyl groups and R is selected from C 6 -C ⁇ 0 aryl groups; wherein R is selected from isopropyl, isobutyl, sec -butyl, tert-butyl and phenyl groups, and R 12 is selected from n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, phenyl, tolyl, benzyl and naphthyl groups; and wherein M 1 is selected from zirconium and hafnium; R and R are
  • R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 and R 24 are each independently selected from hydrogen, halogen and C 1 -C 3 alkyl groups;
  • M represents a carbon or silicon atom.
  • R 13 may selected from di(C ⁇ -C 4 alkyl)silanediyl, diphenylsilanediyl, (C ⁇ -C 4 alkyl)phenylsilanediyl, C -C alkanediyl and alkenediyl, di(C ⁇ -C 4 alkyl)amidoborane and bis[tri(C ⁇ -C alkyl)silyl]amidoborane radicals.
  • metallocenes of this invention are represented by the above formula (I), wherein:
  • M 1 is selected from titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten;
  • R and R are selected from hydrogen, halogen, hydroxy, C 1 -C 10 alkyl groups, Ci- C1 0 alkoxy groups, C -C ⁇ aryl groups, C 6 -C ⁇ 4 aryloxy groups, C -C ⁇ 0 alkenyl groups, C 7 -C 40 arylalkyl groups, C 7 -C 40 alkylaryl groups and C 7 -C 40 arylalkenyl groups; or R and R are joined together to form an alkanediyl group or a conjugated C 4 -C 40 diene ligand which is coordinated to M 1 in a metallacyclopentene fashion; or R and R represent a conjugated diene, optionally substituted with one or more groups independently selected from hydrocarbyl, trihydrocarbylsilyl and trihydrocarbylsilylhydrocarbyl groups, said diene having a total of up to 40 atoms not counting hydrogen and forming a ⁇ complex with M 1 ;
  • each R' is independently selected from halogen, Cj-Cio alkyl groups and C 6 -C ⁇ 4 aryl groups; or two or more adjacent radicals R 5 , R 6 and R 7 together with the atoms connecting them may form one or more rings;
  • R 8 , R 9 , R 10 and R 11 are each independently as defined for R 4 , R 5 , R 6 and R 7 , provided that two or more adjacent radicals R 8 , R 9 , R 1 and R 11 together with the atoms connecting them may form one or more rings;
  • R 12 is selected from halogen, Ci-Cio alkyl groups, C -C ⁇ 4 aryl groups, C 2 -C ⁇ o alkenyl groups, C -C 40 ary
  • R 13 is selected from di(C 6 -Cj 2 aryl))silanediyl, (Cj-C 6 alkyl)(C 6 -C ⁇ 2 aryl)silanediyl, and groups of the formula
  • R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 and R 24 are each independently selected from hydrogen, halogen, hydroxy, C ⁇ -C ⁇ 0 alkyl groups, Cr o alkoxy groups, C 6 -C ⁇ aryl groups, C 6 -C ⁇ 4 aryloxy groups, C 2 -C ⁇ o alkenyl groups, C 7 -C 40 arylalkyl groups, C 7 -C 40 alkylaryl groups and C 8 -C 40 arylalkenyl groups; or two or more adjacent radicals R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 and R 24 , including R 20 and R 21 , together with the atoms connecting them, form one or more rings; and M 2 represents a carbon, silicon or germanium atom.
  • the present invention also provides a catalyst composition which comprises the product of a compound of at least one of the above metallocene compounds of the present invention and a cocatalyst.
  • the cocatalyst may be a compound comprising a noncoordinating anion (e.g., a noncoordinating anion comprising at least one unit of the formula -B(C 6 F 5 ) 3 ) and/or may be an alumoxane, e.g., methylalumoxane.
  • the catalyst composition may comprises a support material, e.g., an inorganic material such as silica, alumina, silica- alumina and magnesium chloride.
  • Preferred support materials include silica having a surface area ranging from 10 to 700 m 2 /g, a total pore volume ranging from 0.1 to 4.0 cc/g and an average particle size ranging from 10 to 500 ⁇ m.
  • Another aspect of the present invention is a polymerization process which comprises contacting, under polymerization conditions, one or more ethylenically unsaturated monomers and a catalyst composition as defined above.
  • the ethylenically unsaturated monomers preferably are selected from monoolefms, diolefins and mixtures thereof
  • Preferred monoolefms include ethylene and ⁇ -olefins having from 3 to 12 carbon atoms such as, e.g., propylene, 1-butene, 4-methyl-l-pentene, 1-hexene, 1-octene and mixtures thereof.
  • the ethylenically unsaturated monomers consist essentially of ethylene and propylene.
  • the temperature ranges from about 30° C to about 80° C. In another aspect, the process is carried out at a pressure ranging from about 5 to about 64 bar.
  • the present invention also provides a polymer composition comprising:
  • Component (a) may be a homopolypropylene or a copolymer of propylene and at least one monoolefin selected from ethylene and ⁇ -olefms having from 4 to 12 carbon atoms, the copolymer containing at least about 99.5 % by weight of units derived from propylene.
  • Component (b) may contain from about 30 to about 60 % by weight of ethylene and/or components (a) and (b) together may contain a total of about 1.5 to about 20 % by weight of ethylene.
  • component (a) has a melting point of at least about 156°C, more preferred at least about 157° C, and/or component (b) has an intrinsic viscosity of at least about 2.0, more preferred at least about 2.2.
  • the composition preferably has a molecular weight distribution, M w /M n , of not higher than about 3.5, more preferably not higher than about 3.0.
  • the catalyst composition used to make the polymer composition is based on a bridged zirconocene compound.
  • a reference to a compound or component includes the compound or component by itself, its individual stereoisomers and any mixtures thereof, of as well as any combination with other compounds or components, such as mixtures of compounds.
  • the term "product" in connection with the catalyst composition of the present invention includes any species that is different in any respect from the completely independent and individual materials, i.e., the metallocene compound
  • catalyst precursor and the cocatalyst (activator).
  • these individual materials may have interacted or even reacted, giving rise to a contact product and/or reaction product.
  • alkyl means a straight-chain, branched-chain or cyclic alkyl radical.
  • examples of such radicals include, but are not limited to, methyl, ethyl, n- propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, 2-ethylhexyl, octyl, cyclopentyl, cyclohexyl and the like.
  • the cyclic alkyl radicals may be substituted with one or more straight-chain and/or branched-chain alkyl radicals (i.e., may be alkylcycloalkyl radicals such as , e.g., methylcyclohexyl etc.).
  • the straight-chain and branched-chain alkyl radicals may be substituted with one or more cyclic alkyl radicals (i.e., may be cycloalkylalkyl radicals such as cyclohexylmethyl etc.).
  • alkyl radicals may be substituted by one or more groups preferably and independently selected from halogen (e.g., F, CI, Br), alkoxy (e.g., methoxy, ethoxy, propoxy, butoxy and the like), hydroxy, amino, monoalkylamino (e.g., methylamino, ethylamino, propylamino and the like) and.
  • halogen e.g., F, CI, Br
  • alkoxy e.g., methoxy, ethoxy, propoxy, butoxy and the like
  • hydroxy amino
  • monoalkylamino e.g., methylamino, ethylamino, propylamino and the like
  • dialkylamino e.g., dimethylamino, diethylamino, dipropylamino, diisopropylamino, piperidino and the like
  • trihydrocarbylsilyl e.g., trimethylsilyl, triphenylsilyl and the like.
  • alkenyl means "alkyl” as defined above having one or more double and/or triple bonds.
  • alkenyl radicals include, but are not limited to, ethenyl, propenyl, allyl, butenyl, propargyl, 1 ,4-butadienyl, isopropenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl, cyclopentadienyl, cyclohexadienyl, cyclooctadienyl and the like.
  • alkoxy means an alkyl or alkenyl ether radical wherein the terms “alkyl” and “alkenyl” are as defined above.
  • suitable alkyl ether radicals include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, allyloxy, trifluoromethoxy and the like.
  • aryl means an aromatic radical, for example, a phenyl, naphthyl, azulenyl, phenanthryl or anthracenyl radical and the like which optionally contains one or more (e.g., 2 or 3) heteroatoms (preferably selected from N, O and S and combinations thereof) in the ring and/or carries one or more identical or different substituents, for example, alkoxy, aryl, halogen, hydroxy, amino, monoalkylamino, dialkylamino, nitro, trihydrocarbylsilyl, alkyl-CO, alkylsulfonyl, alkyl-OCO etc., these terms being as defined herein.
  • aryl radicals are phenyl, naphthyl, fluorenyl, chlorophenyl, dichlorophenyl, fluorophenyl, perfluorophenyl, hydroxyphenyl, anisyl, biphenyl, nitrophenyl, acetylphenyl, aminophenyl, pyridyl, pyridazyl, quinolyl, and the like.
  • aryl radicals When carbon numbers are given herein for aryl radicals, ring heteroatoms are counted as carbon atoms.
  • aryloxy means an aryl ether radical wherein the term “aryl” is as defined above.
  • alkylaryl means an aryl radical carrying at least one alkyl and/or alkenyl radical as ring substituent, the terms “aryl”, “alkyl” and “alkenyl” being as defined above.
  • alkylaryl groups are tolyl, xylyl, mesityl, ethylphenyl, trifluoromethylphenyl, vinylphenyl, cumyl, methylpyridyl and the like.
  • arylalkyl means an alkyl radical carrying at least one aryl group wherein the terms “aryl” and “alkyl” are as defined above, provided that the aryl radical may have one or more alkyl substituents.
  • arylalkyl groups are benzyl, phenethyl, diphenylmethyl, tolylmethyl, naphthylmethyl and the like.
  • arylalkenyl means an alkenyl radical carrying at least one aryl substituent wherein the terms “aryl” and “alkenyl” are as defined above, provided that the aryl radical may have one or more alkyl substituents.
  • Illustrative, non- limiting examples of arylalkenyl groups are styryl, methylstyryl, phenylpropenyl, l-phenyl-l,4-butadienyl and the like.
  • halogen means fluorine, chlorine, bromine and iodine.
  • hydrocarbyl encompasses alkyl, alkenyl, arylalkyl ; arylalkenyl and alkylaryl groups as defined above.
  • Preferred hydrocarbyl groups comprise 1 to 20, more preferred 1 to 10, and most preferred 1 to 6 carbon atoms.
  • Illustrative, non-limiting examples are methyl, ethyl, propyl and phenyl.
  • Alkyl linear and branched alkyl groups having 1 to 8, particularly 1 to 6, and even more preferred, 1 to 4 carbon atoms (such as, e.g., methyl, ethyl, propyl and isopropyl). If present, substituents are preferably selected from halogen and alkoxy, more preferred from F, CI, methoxy and ethoxy, most preferred from F and CI.
  • Alkoxy the preferred alkyl groups connected to an oxygen atom, more preferred methoxy and ethoxy.
  • Alkenyl linear and branched alkenyl groups having 2 to 8, particularly 2 to 6, and even more preferred, 2 to 4 carbon atoms (such as, e.g., vinyl, allyl, and 2-butenyl). If present, substituents are preferably selected from halogen and alkoxy, more preferred from F, CI, methoxy and ethoxy, most preferred from F and Cl.
  • Aryl aryl groups containing 6 to 12, more preferred 6 to 10 carbon atoms, such as, e.g., phenyl, naphthyl and biphenyl. Preferably no heteroatoms are present in the ring system. If present, substituents are preferably selected from halogen and alkoxy, more preferred from F, CI, methoxy and ethoxy, most preferred from F and CI.
  • Aryloxy the preferred aryl groups attached to an oxygen atom. Most preferred are phenoxy and naphthoxy.
  • Arylalkyl and alkylaryl the preferred aryl groups in combination with the preferred alkyl groups, the total number of carbon atoms being 7 to 20, more preferred 7 to 12. Particularly preferred examples include benzyl, phenethyl, tolyl and xylyl.
  • Arylalkenyl the preferred aryl groups in combination with the preferred alkenyl groups, the total number of carbon atoms being 8 to 20, more preferred 8 to 12. Particularly preferred examples include styryl and chlorostyryl.
  • Halogen F, CI and Br, more preferred F and CI.
  • alkyl means an alkyl group as defined above, preferred meanings thereof being also as defined above.
  • M 1 titanium, zirconium, hafnium; more preferred are zirconium and hafnium, with zirconium being most preferred.
  • R and R halogen (more preferred CI and Br), alkyl (more preferred methyl and neopentyl), aryl (more preferred phenyl), alkylaryl (more preferred tolyl) and arylalkyl (more preferred benzyl); or R 1 and R 2 are joined together to form a C 4 - 6 alkanediyl group or a conjugated C 4 -C 6 diene ligand which is coordinated to M 1 in a metallacycloalkane or -cycloalkene fashion; or R 1 and R 2 represent a conjugated diene, optionally substituted with one or more groups independently selected from alkyl, aryl, trialkylsilyl and trialkylsilylalkyl groups, said diene having a total of up to 30, e.g., up to 24 atoms not counting hydrogen and forming a ⁇ complex with M 1 .
  • halogen more preferred CI and Br
  • alkyl more preferred methyl and n
  • conjugated dienes are l,4-diphenyl-l,3-butadiene, 1,3-pentadiene, 2-methyl-l,3- pentadiene, 2,4-hexadiene, 1 -phenyl- 1,3-pentadiene, l,4-dibenzyl-l,3-butadiene,
  • R 1 and R 2 may be different, they are preferably the same.
  • the most preferred meanings of R and R are CI and methyl.
  • R alkyl, aryl, alkylaryl and arylalkyl. More preferred meanings are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, phenyl, naphthyl, tolyl and benzyl, even more preferred isopropyl, benzyl and phenyl. Most preferred is isopropyl.
  • R 4 , R 5 , R 6 and R 7 hydrogen, alkyl and aryl (particularly phenyl), more preferred hydrogen and alkyl.
  • Illustrative, non-limiting examples are hydrogen, methyl and ethyl.
  • R a particularly preferred meaning is hydrogen.
  • all of R 4 , R 5 , R 6 and R 7 are hydrogen.
  • R 8 , R 9 , R 10 and R 11 hydrogen, alkyl, arylalkyl (particularly benzyl) and aryl (particularly phenyl), more preferred hydrogen and alkyl.
  • Illustrative, non- limiting examples are hydrogen, methyl and ethyl.
  • R 8 a particularly preferred meaning is hydrogen.
  • all of R 8 , R 9 , R 10 and R u are hydrogen.
  • at least one of R 9 and R 1 ' is different from hydrogen, it is particularly preferred for R 1 ' to be different from hydrogen when R represents methyl or ethyl.
  • R 12 alkyl, aryl, alkylaryl, arylalkyl and trialkylsilyl. More preferred meanings are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert- butyl, phenyl, naphthyl, (o-, m- and p-)tolyl, benzyl and trimethylsilyl, in particular, isopropyl and phenyl. Most preferred is phenyl.
  • R 13 dialkylsilanediyl, diarylsilanediyl, (aryl)(alkyl)silanediyl, amidoborane, alkylene, arylalkylene and arylene, the latter groups being derived from the defined alkyl, arylalkyl and aryl radicals. More preferred as alkyl and aryl groups are methyl, ethyl, propyl, butyl and phenyl. More preferred alkylene, arylalkylene and arylene radicals are ethylene, propylene, butylene, phenylmethylene and diphenylmethylene as well as phenylene.
  • dialkylsilanediyl, diarylsilanediyl and (aryl)(alkyl)silanediyl radicals are dimethylsilanediyl, diethylsilanediyl, dipropylsilanediyl, dibutylsilanediyl, methylphenylsilanediyl and diphenylsilanediyl.
  • More preferred amidoborane radicals are dialkylamidoborane, diarylamidoborane and bis(trialkylsilyl)- amidoborane radicals.
  • Illustrative, non-limiting examples thereof are dimethyl- amidoborane, diethylamidoborane, diisopropylamidoborane, diphenylamido- borane and bis(trimethylsilyl)amidoborane.
  • Other preferred meanings of R are 9- fluorenyl and 9-silafluorenyl. R is usually connected to the 1 -positions of the indenyl ring systems.
  • 9-silafluorendiylbis [ i-[ 2-methyl, 4-(2-n-propylphenyl)indenyl] ⁇ zirconium dichloride; 9-silafluorendiylbis 2-ethy 1, 4-(2-n-propylpheny l)indenyl] ⁇ zirconium dichloride;
  • 1,4-diphenyl-l ,3-butadiene dimethylsilanediylbis ⁇ 1 - [2-phenyl, 4-(2-ethylphenyl)indeny 1] ⁇ zirconium ⁇ 4 - 1 ,4- diphenyl-l,3-butadiene; dimethylsilanediylbis! 1 -[2-n-propyl, 4-(2-n-propylphenyl)indenyl] ⁇ zirconium ⁇ 4 -
  • 4-(2 -methy lphenyl)indenyl] ⁇ zirconium dichloride represents rac- dimethylsilanediylbis! l -[2-n-propyl, 4-(2-methy lpheny l)indenyl] ⁇ zirconium dichloride, meso- dimethylsilanediylbis! 1 -[2-n-propyl, 4-(2- methylphenyl)indenyl] ⁇ zirconium dichloride and any mixtures of these compounds.
  • metallocenes of this invention are prepared according to general techniques known from the literature, for example U.S. Patent Nos. 5,789,634 and 5,840,644 (both fully incorporated herein by reference).
  • an alkyl anion e.g. n-BuLi
  • an appropriate bridging precursor e.g. Me 2 SiCl 2
  • the final product is purified by column chromatography or distillation; and (c) is double deprotonation via an alkyl anion (e.g. n-BuLi) to form a dianion followed by reaction with a metal halide (e.g.
  • the metallocenes of this invention are highly active catalyst components for the polymerization of olefins. They can form different stereoisomers and are preferably employed as chiral racemates. However, it is also possible to use the individual enantiomers in the (+) or (-) form. The individual stereoisomers allow - an optically active polymer to be prepared. In some cases it may be desirable to remove the meso form of the metallocenes, since the polymerization-active center (the metal atom) in these compounds is no longer chiral due to the mirror symmetry at the central metal atom and it is, therefore, not possible to produce a highly isotactic polymer.
  • racemic metallocenes contaminated with not more than about 5 %, preferably not more than about 2 %, and even more preferred not more than about 1%, of the meso form represent a particularly preferred embodiment of the metallocenes of the present invention.
  • the meso form of a metallocene of the present invention is contaminated with not more than about 5 %, preferably not more than about 2 %, and even more preferred not more than about 1%, of the racemic form.
  • M 2 and R 17 to R 24 are as defined above.
  • Metallocenes are generally used in combination with some form of activator in order to create an active catalyst system.
  • activator and
  • catalyst are used interchangeably and are defined herein to mean any compound or component, or combination of compounds or components, capable of enhancing the ability of one or more metallocenes to polymerize olefins.
  • Alkylalumoxanes such as methylalumoxane (MAO) are commonly used as metallocene activators.
  • the alumoxanes which may be employed according to the present invention are not particularly limited. They include oligomeric linear and/or cyclic alkylalumoxanes of the general formula R-(Al(R)-O) n -AlR 2 for oligomeric, linear alumoxanes and (-Al(R)-O-) m for oligomeric cyclic alumoxanes wherein n usually is 1-40, preferably 10-20, m usually is 3-40, preferably 3-20, and R usually is a CpC 8 alkyl group (e.g., methyl, ethyl, n-propyl, isopropyl, n- butyl and isobutyl), and preferably methyl to provide methylalumoxane (MAO).
  • MAO is a mixture of oligomers with a very wide distribution of molecular weights and usually with an average molecular weight of about 1200. MAO is typically kept in solution in toluene. It is also possible to use, for the present purpose, alumoxanes of the type just described wherein the alkyl groups in the above general formulae are different. A preferred example thereof is modified methylalumoxane (MMAO) wherein in comparison to MAO a part of the methyl groups is replaced by other alkyl groups.
  • MMAO modified methylalumoxane
  • Alumoxane solutions, particularly methylalumoxane solutions may be obtained from commercial vendors as solutions having various concentrations.
  • the atomic ratio of Al in the alumoxane to metal in the metallocene compound is at least about 10 : 1 , more preferably at least about 50 : 1 , and most preferred at least about 80 : 1.
  • said ratio is generally not higher than about 1 ,000 : 1 , particularly not higher than about 500 : 1, with a ratio of not higher than about 300 : 1 being particularly preferred.
  • Ionizing activators may also be used to activate metallocenes. These activators are neutral or ionic, or are compounds such as tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, which ionize the neutral metallocene compound. Unlike alumoxane cocatalysts, these ionizing activators can usually be employed in a molar ratio with respect to the metallocene which is much closer to 1 :1 (e.g., less than 5:1, less than 2:1, and preferably about 1 :1).
  • Such ionizing compounds may contain an active proton, or some other cation associated with, but not coordinated or only loosely coordinated to, the remaining ion of the ionizing compound.
  • Combinations of activators may also be used, for example, alumoxane and ionizing activator combination, see for example, WO 94/07928 (incorporated herein by reference in its entirety).
  • ionic catalysts for coordination polymerization comprised of metallocene cations activated by noncoordinating anions appear in the early work in EP-A-0 277 003, EP-A-0 277 004 and U.S. Patent No. 5,198,401 and WO-A-92/00333 (each fully incorporated herein by reference). These teach desirable methods of preparation wherein metallocenes are protonated by an anion precursor such that an alkyl/hydride group is abstracted from a transition metal to make it both cationic and charge-balanced by the non-coordinating anion.
  • Suitable ionic salts include tetrakis-substituted borate or aluminum salts having fluorinated aryl -constituents such as phenyl, biphenyl and naphthyl.
  • noncoordinating anion means an anion which either does not coordinate to said cation or which is only weakly coordinated to said cation thereby remaining sufficiently labile to be displaced by a neutral Lewis base.
  • “Compatible” non-coordinating anions are those which are not degraded to neutrality when the initially formed complex decomposes. Further, the anion will not transfer an anionic substituent or fragment to the cation so as to cause it to form a neutral four coordinate metallocene compound and a neutral by-product from the anion.
  • Non-coordinating anions useful in accordance with this invention are those which are compatible, stabilize the metallocene cation in the sense of balancing its ionic charge at +1, yet retain sufficient lability to permit displacement by an ethylenically or acetylenically unsaturated monomer during polymerization.
  • ionizing ionic compounds not containing an active proton but capable of producing both the active metallocene cation and a non-coordinating anion. See, for example, EP-A-0 426 637 and EP-A- 0 573 403 (each fully incorporated herein by reference).
  • An additional method of making the ionic catalysts uses ionizing anion precursors which are initially neutral Lewis acids but form the cation and anion upon ionizing reaction with the metallocene compounds, for example the use of tris(pentafluorophenyl)borane. See EP-A-0 520732 (incorporated herein by reference in its entirety).
  • Ionic catalysts for addition polymerization can also be prepared by oxidation of the metal centers of transition metal compounds by anion precursors containing metallic oxidizing groups along with the anion groups, see EP-A-0 495 375 (fully incorporated herein by reference).
  • metal ligands include halogen moieties (for example, chloride) which are not capable of ionizing abstraction under standard conditions, they can be converted via known alkylation reactions with organometallic compounds such as lithium or aluminum hydrides or alkyls, alkylalumoxanes, Grignard reagents, etc. See EP-A-0 500 944 and EP-A1-0 570 982 (each fully incorporated herein by reference) for in situ processes describing the reaction of alkyl aluminum compounds with dihalo-substituted metallocene compounds prior to or with the addition of activating anionic compounds.
  • organometallic compounds such as lithium or aluminum hydrides or alkyls, alkylalumoxanes, Grignard reagents, etc.
  • the activator for the metallocene supported catalyst composition is a NCA
  • the NCA is first added to the support composition followed by the addition of the metallocene catalyst.
  • the activator is MAO
  • the MAO and metallocene catalyst are dissolved together in solution.
  • the support is then contacted with the MAO/metallocene catalyst solution.
  • the catalyst compositions of this invention preferably comprise a support.
  • Suitable supports include porous particulate materials, such as for example, talc, inorganic oxides, inorganic chlorides such as magnesium chloride, and resinous materials such as polyolefins or other polymers.
  • the support materials are porous inorganic oxide materials, which include those from the Periodic Table of Elements of Groups 2, 3, 4, 5, 13 or 14 metal/metalloid oxides.
  • Silica, alumina, silica-alumina, and mixtures thereof are particularly preferable.
  • Other inorganic oxides that may be employed either alone or in combination with the silica, alumina or silica-alumina are magnesia, titania, zirconia, and the like.
  • the support material is porous silica, more preferably porous silica which has a surface area in the range of not less than 10, preferably not less than 50, and most preferred not less than 100 m 2 /g , but usually not more than 700, preferably not more than 500, and most preferred not more than 400 m 2 /g.
  • the total pore volume thereof usually is not less than 0.1, preferably not less than 0.5, and most preferred not less than 0.8 cc/g, whereas the pore volume generally is not higher than 4.0, preferably not higher than 3.5, most preferred not higher than 3.0 cc/g.
  • the average particle size of the porous silica should be at least 10, preferably at least 20, and most preferred at least 30 ⁇ m, the maximum value thereof usually being not higher than 500, preferably not higher than 200, and most preferred not higher than 100 ⁇ m.
  • the average pore size of typical porous support materials usually is at least 10, preferably at least 50, and even more preferably at least 75 A.
  • Average pore sizes should generally not be higher than 1000, preferably not higher than 500, and most preferred not higher than 350 A. It may be particularly desirable to dehydrate the silica at a temperature of from 100°C to 800°C anywhere from 3 to 24 hours.
  • the metallocene, activator and support material may be combined in any number of ways. More than one metallocene may also be used. Examples of suitable support techniques are described in U. S. Patent Nos. 4,808,561 and
  • metallocene and activator are combined and their contact product is supported on the porous support material as described in U. S. Patent No. 5,240,894 and WO 94/28034, WO 96/00243, and WO 96/00245 (each fully incorporated herein by reference).
  • the metallocenes may be preactivated separately and then combined with the support material either separately or together. If the metallocenes are separately supported, then preferably, they are dried and then combined as a powder before use in polymerization.
  • the total volume of reaction solution applied to the porous support is less than 4 times the total pore volume of the porous support, more preferably less than 3 times the total pore volume of the porous support and even more preferably in the range of from more than 1 to less than 2.5 times the total pore volume of the porous support.
  • Procedures for measuring the total pore volume of porous support are well known in the art. One such method is described in Volume 1, Experimental Methods in Catalyst Research, Academic Press, 1968, pages 67-96, fully incorporated herein by reference.
  • the supported catalyst system may be used directly in polymerization or the catalyst system may be prepolymerized using methods well known in the art.
  • the metallocene catalyst systems described herein are useful in the polymerization of all types of olefins. This includes polymerization processes which produce homopolymers, copolymers, terpolymers and the like as well as block copolymers and impact copolymers. These polymerization processes may be carried out in solution, in suspension or in the gas phase, continuously or batchwise, or any combination thereof, in one or more steps, usually at a temperature not lower than 30, preferably not lower than 50, most preferred not lower than 80° C, and not higher than 200, preferably not higher than 120, most preferred not higher than 100°C.
  • R a and R b are identical or different and are a hydrogen atom or an alkyl or alkenyl radical having 1 to 14 carbon atoms.
  • R a and R b may form a ring together with the carbon atoms connecting them.
  • olefins are ethylene, propylene, 1-butene, 1-hexene, 4-methyl-l-pentene, and 1- octene, vinylcyclohexane, norbornene and norbornadiene.
  • propylene and ethylene are polymerized.
  • the metallocenes and metallocenes catalyst systems of this invention are most suitable for the polymerization of propylene based polymers.
  • the overall pressure in the polymerization system usually is at least about 0.5 bar, preferably at least about 2 bar, most preferred at least about 5 bar. Pressures higher than about 100, e.g., higher than about 80 bar and, in particular, higher than about 64 bar are usually not preferred.
  • the metallocene is used in the polymerization in a concentration, based on the transition metal, of not less 10 "4 , preferably not less than 10 "3 mol, and not higher than 10 7 , preferably not higher than 10 4 mol, of transition metal per dm of solvent or per dm of reactor volume.
  • alumoxane When alumoxane is used as the cocatalyst, it is used in a concentration of usually not less than 10 "4 ,preferably not less than 10 " mol, and not higher than 10 " , preferably not higher than 10 " mol, per dm of solvent or per dm of reactor volume.
  • the other cocatalysts mentioned are used in an approximately equimolar amount (e.g., from about 1.2 : 1 to about 1 : 1.2) with respect to the metallocene. In principle, however, higher concentrations are also possible.
  • the polymerization is carried out as a suspension or solution polymerization
  • an inert solvent which is customary for the Ziegler low-pressure process is typically used for example
  • the polymerization is carried out in an aliphatic or cycloaliphatic hydrocarbon; examples of which are propane, butane, hexane, heptane, isooctane, cyclohexane and methylcyclohexane. It is also possible to use mineral spirit or a hydrogenated diesel oil fraction. Toluene can also be used.
  • the polymerization is preferably carried out in the liquid monomer(s). If inert solvents are used, the monomer(s) is (are) metered in gas or liquid form.
  • another alkylaluminum compound such as, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum or isoprenylaluminum, may additionally be introduced into the reactor in order to render the polymerization system inert (for example to remove catalyst poisons present in the olefin).
  • This compound is added to the polymerization system in a concentration of from 100 to 0.01 mmol of Al per kg of reactor contents.
  • the process according to the invention is distinguished by the fact that the metallocenes described can give propylene polymers of very high molecular weight, melting point, and very high stereotacticity, with high catalyst activities in, e.g., the temperature range from about 40°C to about 100°C, such as the industrially particularly interesting polymerization temperature range of from about 50°C to about 80°C .
  • the catalyst systems of this invention are capable of providing polymers, particularly propylene homopolymers and copolymers, of exceptionally high molecular weight and melting point even when used in processes under commercially relevant conditions of temperature, pressure and catalyst activity.
  • Preferred melting points of olefin polymers comprising at least about 99 % by weight, preferably are at least about 99.3 % by weight and most preferred at least 99.5 % by weight of units derived from propylene (the remainder being preferably derived from one or more compounds selected from ethylene and 1 -olefins comprising 4 to 12 carbon atoms, most preferred ethylene) are as high as 155°C, e.g., as high as 156°C, more preferably at least 157°C, even more preferably at least 158°C, and may be as high as 160°C or even higher (these melting points being determined by DSC according to the procedure described in the Examples below).
  • copolymers made with the catalyst systems of the present invention such as, e.g., ethylene/propylene rubbers (EPR's) or ethylene/propylene/diene copolymers (EPDM's), usually have an intrinsic viscosity, measured in decalin at 135° C, of usually at least about 1.8, preferably at least about 2.0, and more preferred at least about 2.1 (e.g., at least about 2.2).
  • EPR's ethylene/propylene rubbers
  • EPDM's ethylene/propylene/diene copolymers
  • the copolymers generally will have an ethylene content of at least about 30, preferably at least about 35, more preferred at least about 40 weight % and not more than about 60, preferably not more than about 50 weight %.
  • the ethylene content of the ICP's usually will be at least about 1.5, preferably at least about 3 weight percent and up to about 20, preferably up to about 15, weight %.
  • the homo- and copolymers made with the catalyst systems of the present invention also have a narrow molecular weight distribution, M w /M n , usually of not higher than about 3.5, preferably not higher than about 3.0, more preferred not higher than about 2.5 and sometimes even not higher than about 2.2. They also are distinguished by low xylene and n-hexane extractables contents. Often the xylene extractables and/or the n-hexane extractables of these homo- and copolymers will amount to less than about 2.0, preferably less than about 1.5, even more preferred less than about 1.0 weight %.
  • a general description of the procedure for measuring the xylene extractables (solubles) is found in J. C. Randall, J. Poly.
  • Hexane extractions are performed by weighing the polymer sample in a dried soxhlet thimble. Hexane is heated to reflux through the thimble in the soxhlet apparatus. When the extraction is complete the solvent is evaporated, and the sample dried under the appropriate vacuum. The amount of extractables is determined by weight. The thimble containing the insoluble polymer is dried in a vacuum oven and the weight of the recovered polymer is determined.
  • the polymer compositions of the present invention are also characterized by a relatively narrow molecular weight distribution.
  • Their values of M w /M n usually are not higher than about 3.5, often not higher than about 3.0, e.g., not higher than about 2.7.
  • Catalyst systems of this invention are capable of providing propylene polymers having high stereospecificity and regiospecificity.
  • Isotactic propylene polymers prepared according to the processes of this invention may have a proportion of 2,1 -inserted propene units of less than about 0.5%, at a triad tacticity of greater than about 98% (see, for example, the results summarized in Table 21C, below).
  • triad tacticity Preferably, there is no measurable proportion of 2,1 -inserted propene units.
  • Triad tacticity is determined using C-NMR according to J.C. Randall,
  • Polymers prepared using the processes described herein find uses in all applications including fibers, injection-molded parts, films, pipes, and wire and cable applications.
  • Non-limiting examples include carpet fibers and primary and secondary carpet backing; slit tape applications such as tarpaulins, erosion abatement screens, sand bags, fertilizer and feed bags, swimming pool covers, intermediate bulk container (IBC) bags; non-woven applications for spunbonded, melt blown and thermobonded carded web applications such as disposable diaper liners, feminine hygiene products, tarpaulins and tent fabrics, and hospital garments; apparel applications such as socks, T-shirts, undergarments, bicycle shorts, sweat bands, football undershirts, hiking socks and other outdoor sporting apparel; cordage applications such as mooring and towing lines and rope applications; netting applications such as safety fences, geogrids for soil stabilization; injection molded applications such as appliance parts in automatic dishwashers and clothes washers, hand tools and kitchen appliances; consumer product applications such as outdoor furniture, luggage, infant car seats, ice coolers, yard equipment;
  • Racemic dimethylsilanediylbis! 1 -[2-methyl, 4-phenylindenyl] ⁇ zirconium dichloride was obtained from commercial sources and used as received.
  • racemic dimethylsilanediylbis! 1 -[2- methyl, 4-phenylindenyl] ⁇ zirconium dichloride (0.055 g) was added to the above MAO solution (6.74 g, 7.2 mL) and stirred twenty minutes. The resultant mixture was filtered through a medium glass frit funnel and washed with toluene (14 mL).
  • dehydrated silica (4.0 g, Davison 948 Regular, 600°C dehydration). This slurry was stirred for twenty minutes then dried at 40 °C for two minutes under vacuum on a rotary evaporator until the liquid evaporated and then the solid was further dried a total of about 2 hours and twenty two minutes.
  • the supported catalyst was recovered as a light orange, free flowing solid (5.63 g).
  • NiCl 2 (PPh 3 ) 2 (1.8 g, 2.8 mmol) and 4-chloro-2-methylindene (9.5 g, 58 mmol) were dissolved in 150 mL of Et 2 O.
  • the Grignard solution was added dropwise to this solution and allowed to stir overnight at reflux. After overnight stirring, the reaction was slowly quenched with H 2 O to neutralize unreacted Grignard.
  • the solution was subsequently treated with 100 mL of 10% HCl(aq), and neutralized with saturated sodium bicarbonate aqueous solution.
  • the organic layer was dried with magnesium sulfate and the solvent removed by rotary evaporation. The remaining residue was loaded onto a silica gel column and eluted with hexane.
  • Me 2 SiCl 2 (1.3 g, 10 mmol) was dissolved in 80 mL of pentane and 60 ml of THF. While stirring, lithium ⁇ l -[2-methyl, 4-(2-methylphenyl)-indenide] ⁇ (4.6 g, 20 mmol) was added as a dry powder and the contents were allowed to stir at reflux for 4 hours. The solvent was removed in vacuo and the residue was taken up in pentane and filtered to remove LiCl salts. The pentane was removed in vacuo, and the crude product was isolated as a viscous oil. Yield: 3.5 g (69 %).
  • dimethylsilanediylbis ⁇ l-[2-methyl,4-(2- methylphenyl)indenyl] ⁇ zirconium dichloride (0.058 g) was added to the above MAO-toluene solution (6.74 g, 7.35 mL) and stirred for twenty minutes.
  • the resultant mixture was filtered through a medium glass frit funnel and washed with toluene (14 mL).
  • dehydrated silica 4.0 g, Davison 948 Regular, 600°C dehydration).
  • This slurry was stirred for twenty minutes, then dried at 40 °C for two minutes under vacuum on a rotary evaporator until the liquid evaporated and then the solid was further dried a total of about 2 hours and thirty two minutes.
  • the supported catalyst was recovered as a salmon orange, free flowing solid (5.34 g).
  • dehydrated silica (4.0 g, Davison 948 Regular, 600°C dehydration). This slurry was stirred for twenty minutes, then dried at 40 °C for two minutes under vacuum on a rotary evaporator until the liquid evaporated and then the solid was further dried a total of about two hours and thirty three minutes.
  • the supported catalyst was recovered as a pink, free flowing solid (5.57 g).
  • lithium ⁇ l -[2-methyl, 4-(2-isopropylphenyl)indenide] ⁇ (4.0 g, 15.5 mmol) was added as a dry powder and the contents were allowed to stir overnight at room temperature. The solvent was removed in vacuo and the residue was taken up in pentane and filtered to remove LiCl salts. The pentane was removed in vacuo to yield a flaky white solid (2.1 g, 48 %).

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Abstract

Metallocenes and catalyst systems for olefin polymerization derived therefrom. The metallocenes may be represented by the formula (I), wherein M1 preferably is zirconium or hafnium; and R12 is different from hydrogen.

Description

TITLE: METALLOCENES AND CATALYST COMPOSITIONS DERIVED THEREFROM
FIELD
This invention relates to metallocene compounds and their use in the preparation of catalyst compositions for olefin polymerization, particularly propylene homo- and copolymerization. The present invention also relates to polymerisation processes using such catalyst compositions and polymer compositions obtainable by these processes.
BACKGROUND
The use of metallocene compositions in olefin polymerization is well known. Metallocenes containing substituted, bridged indenyl derivatives are noted for their ability to produce isotactic propylene polymers having high isotacticity and narrow molecular weight distribution. Considerable effort has been made toward obtaining metallocene produced propylene polymers having ever-higher molecular weight and melting point and, thus, ever better strength (impact) properties, while maintaining suitable catalyst activity.
Toward this end researchers have found that there is a direct relationship between the way in which a metallocene is substituted and the molecular structure of the resulting polymer. For the substituted, bridged indenyl type metallocenes, it is now well established that the type and arrangement of substituents on the indenyl groups, as well as the type of bridge connecting the indenyl groups, determines such polymer attributes as molecular weight and melting point. indenyl groups, as well as the type of bridge connecting the indenyl groups, determines such polymer attributes as molecular weight and melting point.
For example, U. S. Patent Nos. 5,840,644 and 5,770,753, incorporated herein by reference in their entireties, describe certain metallocenes containing aryl-substituted indenyl derivatives as ligands, which are said to provide propylene polymers having high isotacticity, narrow molecular weight distribution and very high molecular weight.
Likewise, U. S. Patent No. 5,936,053, incorporated herein by reference in its entirety, describes certain metallocene compounds said to be useful for producing high molecular weight propylene polymers. These metallocenes have a specific hydrocarbon substituent at the 2 position and an unsubstituted aryl substituent at the 4 position on each indenyl group of the metallocene compound.
WO 98/40419 and WO 99/42497 both describe certain supported catalyst systems for producing propylene polymers having high melting point. Metallocene compositions and their activators are often combined with a support material in order to obtain a catalyst system that is less likely to cause reactor fouling. However, it is known that supported metallocene catalyst systems tend to result in a polymer having lower melting point than would otherwise be obtained if the metallocene were not supported.
Much of the current research in this area has been directed toward using metallocene catalyst systems under commercially relevant process conditions, to obtain propylene polymers having melting points higher than known metallocene catalyst systems and close to, or as high as, propylene polymers obtained using conventional, Ziegler-Natta catalyst systems. The present inventors have discovered metallocene compounds that not only have this capability, but retain it upon supportation.
Additionally, it would be desirable to have available metallocenes which not only afford propylene homopolymers having high melting points of (i.e., high stereotacticity), but also elastomeric copolymers having the high molecular weights required for the production of, e.g., impact copolymers, thereby making possible the production of satisfactory in situ blends of, e.g., propylene homopolymer and ethylene-propylene rubbers (EPR's) with a single catalyst composition in a single reactor or in a series of two or more reactors. The present inventors have found metallocene compounds which in combination with a cocatalyst (activator) make both propylene homopolymers having high melting points and elastomeric copolymers that are suitable for the production of impact copolymers in combination with these propylene homopolymers.
SUMMARY OF THE INVENTION
The present invention relates to novel metallocene compounds capable of providing propylene homo- and copolymers having high melting point and high molecular weight. The present invention further relates to metallocene catalyst compositions comprising one or more of these compounds and one or more activators or cocatalysts, and optionally, support material, and to the use of such catalyst compositions in polymerization, in particular propylene polymerization.
In one aspect, the present invention provides metallocene compounds represented by formula (I):
Figure imgf000006_0001
wherein:
M1 is selected from titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten;
R1 and R2 are selected from hydrogen, halogen, hydroxy, Cι-Cι0 alkyl groups, C\-
C10 alkoxy groups, C6-C]4 aryl groups, C6-Cι4 aryloxy groups, C -Cιo alkenyl groups, C7-C40 arylalkyl groups, C -C40 alkylaryl groups and C -C40 arylalkenyl
1 ") groups; or R and R are joined together to form a C4-C 0 alkanediyl group or a conjugated diene ligand which is coordinated to M1 in a metallacyclopentene fashion; or R1 and R2 represent a conjugated diene, optionally substituted with one or more groups independently selected from hydrocarbyl, trihydrocarbylsilyl and trihydrocarbylsilylhydrocarbyl groups, said diene having a total of up to 40 atoms not counting hydrogen and forming a π complex with M1;
R3 is selected from hydrogen, halogen, Ci-Cio alkyl groups, C6-Cι4 aryl groups, C2-C)0 alkenyl groups, C -C40 arylalkyl groups, C7-C40 alkylaryl groups, C8-C40 arylalkenyl groups, and -NR'2, -SR', -OR', -SiR* 3, -OSiR'3 and -PR'2 radicals wherein each R' is independently selected from halogen, Ci-Cio alkyl groups and C6-Cι4 aryl groups; provided that if R1 and R2 both are halogen and R13 is dimethylsilanediyl, R3 is different from methyl and ethyl;
R4, R5, R6 and R7 are each independently selected from hydrogen, halogen, Cι-Cι0 alkyl groups, C -Cι4 aryl groups, C2-Cι0 alkenyl groups, C -C40 arylalkyl groups, C7-C40 alkylaryl groups, C8-C40 arylalkenyl groups, and -NR'2, -SR', -OR', -SiR'3, -
OSiR'3 and -PR'2 radicals wherein each R' is independently selected from halogen, C1-C10 alkyl groups and C6-Cι4 aryl groups; or two or more adjacent radicals R5, R6 and R7 together with the atoms connecting them may form one or more rings; R8, R9, R10 and R11 are each independently as defined for R4, R5, R6 and R7, provided that two or more adjacent radicals R8' R9, R10 and R11 together with the atoms connecting them may form one or more rings;
R12 is selected from halogen, CpCio alkyl groups, C6-C14 aryl groups, C2-C10 alkenyl groups, C7-C40 arylalkyl groups, C -C40 alkylaryl groups, C8-C40 arylalkenyl groups, and -NR'2, -SR', -OR', -SiR'3, -OSiR'3 and -PR'2 radicals wherein each R' is independently selected from halogen, C1-C10 alkyl groups and
C6-Cι4 aryl groups; R13 is selected from
Figure imgf000007_0001
I I
-M3- -M3- - M3- -O-M3-O-
I I I
I I I
R15 R15 R15 I
R15
R14 R16 R14 R14 R14 R14
1 1
I I 1 1 1
I 1 1 1 M3- C - - O-M3- - C — C - C —
I I 1 1 1
I I
R15 R16 R 115 R 115 R 115 R 115
-B(R14)-, -A1(R14)-, -Ge-, -Sn-, -O-, -S-, -SO-, -SO2-, -N(R14)-, -CO-, -P(R14)- -
P(O)(R14)-, -B(NR14R15)- and -B[N(SiR14R15R16)2]-; wherein:
R14, R15 and R1 are each independently selected from hydrogen, halogen, Cι-C20 alkyl groups, C6-C30 aryl groups, Cι-C20 alkoxy groups, C2-C20 alkenyl groups, C7-C4o arylalkyl groups, C -C 0 arylalkenyl groups and C7-C 0 alkylaryl groups, or R14 and R15, together with the atom(s) connecting them, form a ring; and M3 is selected from carbon, silicon, germanium and tin; or R is represented by the formula
Figure imgf000008_0001
wherein:
R17, R18, R19, R20, R21, R22, R23 and R24 are each independently selected from hydrogen, halogen, hydroxy, Cι-Cι0 alkyl groups, Cι-Cι0 alkoxy groups, C6-Cι4 aryl groups, C6-Cι4 aryloxy groups, C2-Cιo alkenyl groups, C7-C40 arylalkyl groups, C7-C40 alkylaryl groups and C8-C40 arylalkenyl groups; or two or more adjacent radicals R17, R18, R19, R20, R21, R22, R23 and R24, including R20 and R21, together with the atoms connecting them, form one or more rings; and
M represents one or more carbon atoms, or a silicon, germanium or tin atom.
In preferred embodiments of the above compound, M1 is selected from titanium, zirconium and hafnium and R and R are selected from chlorine, Cι-C6 alkyl groups, C6-C]0 aryl groups, C7-Cι2 arylalkyl groups and C7-Cι2 alkylaryl groups.
R may be a C3-C6 alkyl group such as, e.g., a branched C3-C4 alkyl group and, in particular, an isopropyl group, or may be a phenyl group.
Preferably at least one of R and R , and most preferred both of them, represent hydrogen atoms. - 1 ■
In the above formula, M may be selected from carbon and silicon, and R14, R15 and R16 may independently be selected from C]-C4 alkyl groups and C6- Cio aryl groups. Moreover, when R13 is represented by the formula
Figure imgf000009_0001
R , 1"7, R , 18 , R , 19 , R ,20 , R , R ,22 , W »23i and R 244 may each be hydrogen, with M representing a silicon atom.
R12 may be selected from Cι-C6 alkyl groups and C6-Cι0 aryl groups, a preferred meaning being phenyl. In another embodiment, R11 is different from hydrogen and may represent, e.g., a Cι-C4 alkyl group.
Particularly preferred compounds of the above formula include those wherein R and R are selected from chlorine, methyl, neopentyl and benzyl, R is selected from C3-C4 alkyl groups, each of R4 and R8 is hydrogen, and R12 is selected from Cι-C4 alkyl groups and C6-Cι0 aryl groups; wherein R is selected from branched C3-C alkyl groups and R is selected from C6-Cι0 aryl groups; wherein R is selected from isopropyl, isobutyl, sec -butyl, tert-butyl and phenyl groups, and R12 is selected from n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, phenyl, tolyl, benzyl and naphthyl groups; and wherein M1 is selected from zirconium and hafnium; R and R are selected from chlorine, C1-C3 alkyl groups and C6-Cι0 aryl groups; R is selected from C3-C6 alkyl groups and C6-Cιo aryl groups; R4 and R8 are hydrogen; R5, R6, R7, R9, R10 and R1 1 are each independently selected from hydrogen, halogen and Cι-C3 alkyl groups; R is selected from C3-C6 alkyl groups and C6-C10 aryl groups; and R is selected from di(Cj-C4 alkyl)silanediyl, diphenylsilanediyl, (Cι-C4 alkyl)phenylsilanediyl, diphenylmethanediyl and C2-C alkanediyl and alkenediyl radicals, and groups of the formula
Figure imgf000010_0001
wherein:
R17, R18, R19, R20, R21, R22, R23 and R24 are each independently selected from hydrogen, halogen and C1-C3 alkyl groups; and
M represents a carbon or silicon atom.
In another aspect R13 may selected from di(Cι-C4 alkyl)silanediyl, diphenylsilanediyl, (Cι-C4 alkyl)phenylsilanediyl, C -C alkanediyl and alkenediyl, di(Cι-C4 alkyl)amidoborane and bis[tri(Cι-C alkyl)silyl]amidoborane radicals.
Other preferred compounds of the above formula may comprise not more than 2 % of the meso isomer.
In another aspect the metallocenes of this invention are represented by the above formula (I), wherein:
M1 is selected from titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten;
1 ?
R and R are selected from hydrogen, halogen, hydroxy, C1-C10 alkyl groups, Ci- C10 alkoxy groups, C -Cι aryl groups, C6-Cι4 aryloxy groups, C -Cι0 alkenyl groups, C7-C40 arylalkyl groups, C7-C40 alkylaryl groups and C7-C40 arylalkenyl groups; or R and R are joined together to form an alkanediyl group or a conjugated C4-C40 diene ligand which is coordinated to M1 in a metallacyclopentene fashion; or R and R represent a conjugated diene, optionally substituted with one or more groups independently selected from hydrocarbyl, trihydrocarbylsilyl and trihydrocarbylsilylhydrocarbyl groups, said diene having a total of up to 40 atoms not counting hydrogen and forming a π complex with M1; R is selected from hydrogen, halogen, Cι-C]0 alkyl groups, C6-Cι aryl groups, C2-Cιo alkenyl groups, C -C 0 arylalkyl groups, C7-C40 alkylaryl groups, C8-C 0 arylalkenyl groups, and -NR'2, -SR*, -OR', -SiR'3, -OSiR'3 and -PR'2 radicals wherein each R' is independently selected from halogen, Ci-Cio alkyl groups and C6-Cι aryl groups; R4, R5, R6 and R7 are each independently selected from hydrogen, halogen, Cι-Cι0 alkyl groups, C6-Cι aryl groups, C2-Cι0 alkenyl groups, C -C 0 arylalkyl groups,
C -C40 alkylaryl groups, C8-C40 arylalkenyl groups, and -NR'2, -SR', -OR', -SiR'3, -OSiR'3 and -PR'2 radicals wherein each R' is independently selected from halogen, Cj-Cio alkyl groups and C6-Cι4 aryl groups; or two or more adjacent radicals R5, R6 and R7 together with the atoms connecting them may form one or more rings; R8, R9, R10 and R11 are each independently as defined for R4, R5, R6 and R7, provided that two or more adjacent radicals R8, R9, R1 and R11 together with the atoms connecting them may form one or more rings; R12 is selected from halogen, Ci-Cio alkyl groups, C -Cι4 aryl groups, C2-Cιo alkenyl groups, C -C40 arylalkyl groups, C7-C40 alkylaryl groups, C8-C40 arylalkenyl groups, and -NR'2, -SR', -OR', -SiR'3, -OSiR'3 and -PR'2 radicals wherein each R' is independently selected from halogen, Ci-Cio alkyl groups and C6-C]4 aryl groups;
R13 is selected from di(C6-Cj2 aryl))silanediyl, (Cj-C6 alkyl)(C6-Cι2 aryl)silanediyl, and groups of the formula
Figure imgf000012_0001
wherein:
R17, R18, R19, R20, R21, R22, R23 and R24 are each independently selected from hydrogen, halogen, hydroxy, Cι-Cι0 alkyl groups, Cr o alkoxy groups, C6-Cι aryl groups, C6-Cι4 aryloxy groups, C2-Cιo alkenyl groups, C7-C40 arylalkyl groups, C7-C40 alkylaryl groups and C8-C40 arylalkenyl groups; or two or more adjacent radicals R17, R18, R19, R20, R21, R22, R23 and R24, including R20 and R21, together with the atoms connecting them, form one or more rings; and M2 represents a carbon, silicon or germanium atom.
Preferred embodiments of these compounds are those already given above.
The present invention also provides a catalyst composition which comprises the product of a compound of at least one of the above metallocene compounds of the present invention and a cocatalyst. The cocatalyst may be a compound comprising a noncoordinating anion (e.g., a noncoordinating anion comprising at least one unit of the formula -B(C6F5)3) and/or may be an alumoxane, e.g., methylalumoxane. The catalyst composition may comprises a support material, e.g., an inorganic material such as silica, alumina, silica- alumina and magnesium chloride.
Preferred support materials include silica having a surface area ranging from 10 to 700 m2/g, a total pore volume ranging from 0.1 to 4.0 cc/g and an average particle size ranging from 10 to 500 μm. Another aspect of the present invention is a polymerization process which comprises contacting, under polymerization conditions, one or more ethylenically unsaturated monomers and a catalyst composition as defined above.
The ethylenically unsaturated monomers preferably are selected from monoolefms, diolefins and mixtures thereof Illustrative and non-limiting examples of suitable monoolefms are compounds of the formula RaCH=CHRb wherein Ra and Rb are each independently selected from hydrogen, alkyl and alkenyl radicals having 1 to 14 carbon atoms or, together with the carbon atoms to which they are connected, form a ring having 4 to 8 carbon atoms. Preferred monoolefms include ethylene and α-olefins having from 3 to 12 carbon atoms such as, e.g., propylene, 1-butene, 4-methyl-l-pentene, 1-hexene, 1-octene and mixtures thereof. In a preferred embodiment, the ethylenically unsaturated monomers consist essentially of ethylene and propylene.
In one aspect of the above process the temperature ranges from about 30° C to about 80° C. In another aspect, the process is carried out at a pressure ranging from about 5 to about 64 bar.
The present invention also provides a polymer composition comprising:
(a) propylene polymer comprising at least about 99 % by weight of units derived from propylene and having a melting point of at least about 155° C; and (b) olefin copolymer comprising from about 40 to about 70 % by weight of units derived from propylene and having an intrinsic viscosity of at least about 1.8; the composition made with a single catalyst composition. Component (a) may be a homopolypropylene or a copolymer of propylene and at least one monoolefin selected from ethylene and α-olefms having from 4 to 12 carbon atoms, the copolymer containing at least about 99.5 % by weight of units derived from propylene. Component (b) may contain from about 30 to about 60 % by weight of ethylene and/or components (a) and (b) together may contain a total of about 1.5 to about 20 % by weight of ethylene. In a preferred composition of the present invention component (a) has a melting point of at least about 156°C, more preferred at least about 157° C, and/or component (b) has an intrinsic viscosity of at least about 2.0, more preferred at least about 2.2. The composition preferably has a molecular weight distribution, Mw/Mn, of not higher than about 3.5, more preferably not higher than about 3.0.
In another preferred embodiment the catalyst composition used to make the polymer composition is based on a bridged zirconocene compound.
DETAILED DESCRIPTION
In the following detailed description, unless otherwise stated, all percentages, parts, ratios, etc., are by weight.
Also, unless otherwise stated, a reference to a compound or component includes the compound or component by itself, its individual stereoisomers and any mixtures thereof, of as well as any combination with other compounds or components, such as mixtures of compounds.
Further, when an amount, concentration, or other value or parameter, is given as a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of an upper preferred value and a lower preferred value, regardless whether ranges are separately disclosed.
Additionally, as utilized herein, the following terms have the meanings indicated below.
The term "product" in connection with the catalyst composition of the present invention includes any species that is different in any respect from the completely independent and individual materials, i.e., the metallocene compound
(catalyst precursor) and the cocatalyst (activator). By way of illustrative, non- limiting example, these individual materials may have interacted or even reacted, giving rise to a contact product and/or reaction product.
The term "alkyl", means a straight-chain, branched-chain or cyclic alkyl radical. Examples of such radicals include, but are not limited to, methyl, ethyl, n- propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, 2-ethylhexyl, octyl, cyclopentyl, cyclohexyl and the like. The cyclic alkyl radicals may be substituted with one or more straight-chain and/or branched-chain alkyl radicals (i.e., may be alkylcycloalkyl radicals such as , e.g., methylcyclohexyl etc.). Conversely, the straight-chain and branched-chain alkyl radicals may be substituted with one or more cyclic alkyl radicals (i.e., may be cycloalkylalkyl radicals such as cyclohexylmethyl etc.). Moreover, unless indicated otherwise, the above alkyl radicals may be substituted by one or more groups preferably and independently selected from halogen (e.g., F, CI, Br), alkoxy (e.g., methoxy, ethoxy, propoxy, butoxy and the like), hydroxy, amino, monoalkylamino (e.g., methylamino, ethylamino, propylamino and the like) and. dialkylamino (e.g., dimethylamino, diethylamino, dipropylamino, diisopropylamino, piperidino and the like) and trihydrocarbylsilyl (e.g., trimethylsilyl, triphenylsilyl and the like).
The term "alkenyl" means "alkyl" as defined above having one or more double and/or triple bonds. Examples of alkenyl radicals include, but are not limited to, ethenyl, propenyl, allyl, butenyl, propargyl, 1 ,4-butadienyl, isopropenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl, cyclopentadienyl, cyclohexadienyl, cyclooctadienyl and the like.
The term "alkoxy" means an alkyl or alkenyl ether radical wherein the terms "alkyl" and "alkenyl" are as defined above. Examples of suitable alkyl ether radicals include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, allyloxy, trifluoromethoxy and the like. The term "aryl" means an aromatic radical, for example, a phenyl, naphthyl, azulenyl, phenanthryl or anthracenyl radical and the like which optionally contains one or more (e.g., 2 or 3) heteroatoms (preferably selected from N, O and S and combinations thereof) in the ring and/or carries one or more identical or different substituents, for example, alkoxy, aryl, halogen, hydroxy, amino, monoalkylamino, dialkylamino, nitro, trihydrocarbylsilyl, alkyl-CO, alkylsulfonyl, alkyl-OCO etc., these terms being as defined herein. Illustrative, non-limiting examples of aryl radicals are phenyl, naphthyl, fluorenyl, chlorophenyl, dichlorophenyl, fluorophenyl, perfluorophenyl, hydroxyphenyl, anisyl, biphenyl, nitrophenyl, acetylphenyl, aminophenyl, pyridyl, pyridazyl, quinolyl, and the like. When carbon numbers are given herein for aryl radicals, ring heteroatoms are counted as carbon atoms.
The term "aryloxy" means an aryl ether radical wherein the term "aryl" is as defined above.
The term "alkylaryl" means an aryl radical carrying at least one alkyl and/or alkenyl radical as ring substituent, the terms "aryl", "alkyl" and "alkenyl" being as defined above. Illustrative, non-limiting examples of alkylaryl groups are tolyl, xylyl, mesityl, ethylphenyl, trifluoromethylphenyl, vinylphenyl, cumyl, methylpyridyl and the like.
The term "arylalkyl" means an alkyl radical carrying at least one aryl group wherein the terms "aryl" and "alkyl" are as defined above, provided that the aryl radical may have one or more alkyl substituents. Illustrative, non-limiting examples of arylalkyl groups are benzyl, phenethyl, diphenylmethyl, tolylmethyl, naphthylmethyl and the like.
The term "arylalkenyl" means an alkenyl radical carrying at least one aryl substituent wherein the terms "aryl" and "alkenyl" are as defined above, provided that the aryl radical may have one or more alkyl substituents. Illustrative, non- limiting examples of arylalkenyl groups are styryl, methylstyryl, phenylpropenyl, l-phenyl-l,4-butadienyl and the like.
The term "halogen" means fluorine, chlorine, bromine and iodine.
The term "hydrocarbyl" encompasses alkyl, alkenyl, arylalkyl ; arylalkenyl and alkylaryl groups as defined above. Preferred hydrocarbyl groups comprise 1 to 20, more preferred 1 to 10, and most preferred 1 to 6 carbon atoms. Illustrative, non-limiting examples are methyl, ethyl, propyl and phenyl.
Unless specified otherwise herein, preferred meanings of the various groups defined above are:
Alkyl: linear and branched alkyl groups having 1 to 8, particularly 1 to 6, and even more preferred, 1 to 4 carbon atoms (such as, e.g., methyl, ethyl, propyl and isopropyl). If present, substituents are preferably selected from halogen and alkoxy, more preferred from F, CI, methoxy and ethoxy, most preferred from F and CI.
Alkoxy: the preferred alkyl groups connected to an oxygen atom, more preferred methoxy and ethoxy.
Alkenyl: linear and branched alkenyl groups having 2 to 8, particularly 2 to 6, and even more preferred, 2 to 4 carbon atoms (such as, e.g., vinyl, allyl, and 2-butenyl). If present, substituents are preferably selected from halogen and alkoxy, more preferred from F, CI, methoxy and ethoxy, most preferred from F and Cl.
Aryl: aryl groups containing 6 to 12, more preferred 6 to 10 carbon atoms, such as, e.g., phenyl, naphthyl and biphenyl. Preferably no heteroatoms are present in the ring system. If present, substituents are preferably selected from halogen and alkoxy, more preferred from F, CI, methoxy and ethoxy, most preferred from F and CI.
Aryloxy: the preferred aryl groups attached to an oxygen atom. Most preferred are phenoxy and naphthoxy.
Arylalkyl and alkylaryl: the preferred aryl groups in combination with the preferred alkyl groups, the total number of carbon atoms being 7 to 20, more preferred 7 to 12. Particularly preferred examples include benzyl, phenethyl, tolyl and xylyl.
Arylalkenyl: the preferred aryl groups in combination with the preferred alkenyl groups, the total number of carbon atoms being 8 to 20, more preferred 8 to 12. Particularly preferred examples include styryl and chlorostyryl.
Halogen: F, CI and Br, more preferred F and CI.
Preferred meanings of the various constituents of the compounds of formula (I) above are as follows, it being understood that these preferred meanings are defined as above, including the preferred embodiments of a particular meaning. For example, "alkyl" means an alkyl group as defined above, preferred meanings thereof being also as defined above.
M1 : titanium, zirconium, hafnium; more preferred are zirconium and hafnium, with zirconium being most preferred.
1 7
R and R : halogen (more preferred CI and Br), alkyl (more preferred methyl and neopentyl), aryl (more preferred phenyl), alkylaryl (more preferred tolyl) and arylalkyl (more preferred benzyl); or R1 and R2 are joined together to form a C4-6 alkanediyl group or a conjugated C4-C6 diene ligand which is coordinated to M1 in a metallacycloalkane or -cycloalkene fashion; or R1 and R2 represent a conjugated diene, optionally substituted with one or more groups independently selected from alkyl, aryl, trialkylsilyl and trialkylsilylalkyl groups, said diene having a total of up to 30, e.g., up to 24 atoms not counting hydrogen and forming a π complex with M1. Illustrative, non-limiting examples of conjugated dienes are l,4-diphenyl-l,3-butadiene, 1,3-pentadiene, 2-methyl-l,3- pentadiene, 2,4-hexadiene, 1 -phenyl- 1,3-pentadiene, l,4-dibenzyl-l,3-butadiene,
1,4-ditolyl- 1,3 -butadiene, l,4-bis(trimethylsilyl)-l,3-butadiene, and 1,4- dinaphthyl- 1,3 -butadiene. While R1 and R2 may be different, they are preferably the same. The most preferred meanings of R and R are CI and methyl.
R : alkyl, aryl, alkylaryl and arylalkyl. More preferred meanings are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, phenyl, naphthyl, tolyl and benzyl, even more preferred isopropyl, benzyl and phenyl. Most preferred is isopropyl.
R4, R5, R6 and R7: hydrogen, alkyl and aryl (particularly phenyl), more preferred hydrogen and alkyl. Illustrative, non-limiting examples are hydrogen, methyl and ethyl. For R a particularly preferred meaning is hydrogen. In another preferred embodiment, all of R4, R5, R6 and R7 are hydrogen.
R8, R9, R10 and R11: hydrogen, alkyl, arylalkyl (particularly benzyl) and aryl (particularly phenyl), more preferred hydrogen and alkyl. Illustrative, non- limiting examples are hydrogen, methyl and ethyl. For R8 a particularly preferred meaning is hydrogen. In another preferred embodiment, all of R8, R9, R10 and Ru are hydrogen. While in still another preferred embodiment at least one of R9 and R1 ' is different from hydrogen, it is particularly preferred for R1 ' to be different from hydrogen when R represents methyl or ethyl.
R12: alkyl, aryl, alkylaryl, arylalkyl and trialkylsilyl. More preferred meanings are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert- butyl, phenyl, naphthyl, (o-, m- and p-)tolyl, benzyl and trimethylsilyl, in particular, isopropyl and phenyl. Most preferred is phenyl. R13: dialkylsilanediyl, diarylsilanediyl, (aryl)(alkyl)silanediyl, amidoborane, alkylene, arylalkylene and arylene, the latter groups being derived from the defined alkyl, arylalkyl and aryl radicals. More preferred as alkyl and aryl groups are methyl, ethyl, propyl, butyl and phenyl. More preferred alkylene, arylalkylene and arylene radicals are ethylene, propylene, butylene, phenylmethylene and diphenylmethylene as well as phenylene. More preferred dialkylsilanediyl, diarylsilanediyl and (aryl)(alkyl)silanediyl radicals are dimethylsilanediyl, diethylsilanediyl, dipropylsilanediyl, dibutylsilanediyl, methylphenylsilanediyl and diphenylsilanediyl. More preferred amidoborane radicals are dialkylamidoborane, diarylamidoborane and bis(trialkylsilyl)- amidoborane radicals. Illustrative, non-limiting examples thereof are dimethyl- amidoborane, diethylamidoborane, diisopropylamidoborane, diphenylamido- borane and bis(trimethylsilyl)amidoborane. Other preferred meanings of R are 9- fluorenyl and 9-silafluorenyl. R is usually connected to the 1 -positions of the indenyl ring systems.
The following are particularly preferred metallocenes: dimethylsilanediylbis { 1 - [2-n-propyl, 4-(2-methylphenyl)indenyl] } zirconium dichloride; dimethylsilanediylbis{ l-[2-isopropyl, 4-(2-methylphenyl)indenyl]} zirconium dichloride; dimethylsilanediylbis{ l-[2-n-butyl, 4-(2-methylphenyl)indenyl]} zirconium dichloride; dimethylsilanediylbis{ l-[2-isobutyl, 4-(2-methylphenyl)indenyl]} zirconium dichloride; dimethylsilanediylbis{ l-[2-sec-butyl, 4-(2-methylphenyl)indenyl]}zirconium dichloride; dimethylsilanediylbis { 1 -[2 -tert-butyl, 4-(2-methylphenyl)indenyl]} zirconium dichloride; dimethylsilanediylbis! 1 -[2 -phenyl, 4-(2-methylphenyl)indenyl]} zirconium dichloride; dimethylsilanediylbis 1- 2-n-propyl, 4-(2-ethylphenyl)indenyl] } zirconium dichloride; dimethylsilanediylbis 2-isopropyl, 4-(2-ethylphenyl)indenyl] } zirconium dichloride; dimethylsilanediylbis 2-n-butyl, 4-(2-ethylphenyl)indenyl]} zirconium dichloride; dimethylsilanediylbis 1- 2-isobutyl, 4-(2-ethylphenyl)indenyl] } zirconium dichloride; dimethylsilanediylbis 1- 2-sec-butyl, 4-(2-ethylphenyl)indenyl] } zirconium dichloride; dimethylsilanediylbis 1- 2-tert-butyl, 4-(2-ethylphenyl)indenyl] } zirconium dichloride; dimethylsilanediylbis 1- 2-phenyl, 4-(2-ethylphenyl)indenyl] } zirconium dichloride; dimethylsilanediylbis 1- 2-n-propyl, 4-(2-n-propylphenyl)indenyl] } zirconium dichloride; dimethylsilanediylbis 1- 2-isopropyl, 4-(2-n-propylphenyl)indeny 1] } zirconium dichloride; dimethylsilanediylbis 2-n-butyl, 4-(2-n-propylpheny l)indeny 1] } zirconium dichloride; dimethylsilanediylbis 2-isobutyl, 4-(2-n-propylphenyl)indenyl] } zirconium dichloride; dimethylsilanediylbis 2-sec-butyl, 4-(2-n-propylphenyl)indenyl] } zirconium dichloride; dimethylsilanediylbis 1- 2-tert-butyl, 4-(2-n-propylphenyl)indenyl] } zirconium dichloride; dimethylsilanediylbis 1- 2-phenyl, 4-(2-n-propylphenyl)indenyl] } zirconium dichloride; dimethylsilanediylbis 1- 2-n-propyl, 4-(2-isopropylphenyl)indenyl] } zirconium dichloride; dimethylsilanediylbis 1- 2-isopropyl, 4-(2-isopropylphenyl)indenyl] } zirconium dichloride; dimethylsilanediylbis 1- 2 -n-butyl, 4-(2-isopropylphenyl)indenyl] } zirconium dichloride; dimethylsilanediylbis 1- 2-isobutyl, 4-(2-isopropylpheny l)indeny 1] } zirconium dichloride; dimethylsilanediylbis 2-sec-butyl, 4-(2-isopropylphenyl)indenyl] } zirconium dichloride; dimethylsilanediylbis 1- 2-tert-butyl, 4-(2-isopropy lphenyl)indeny 1] } zirconium dichloride; dimethylsilanediylbis 1- 2-phenyl, 4-(2-isopropylphenyl)indenyl] } zirconium dichloride; dimethylsilanediylbis 1- 2-n-propyl, 4-(2-n-butylphenyl)indenyl] } zirconium dichloride; dimethylsilanediylbis 1- 2-isopropyl, 4-(2-n-butylphenyl)indenyl] } zirconium dichloride; dimethylsilanediylbis 1- 2-n-butyl, 4-(2-n-buty lpheny l)indenyl] } zirconium dichloride; dimethylsilanediylbis 2-isobutyl, 4-(2-n-butylphenyl)indenyl]} zirconium dichloride; dimethylsilanediylbis 2-sec-butyl, 4-(2-n-butylphenyl)indenyl]} zirconium dichloride; dimethyl silanediy Ibi s 2-tert-butyl, 4-(2-n-butylphenyl)indenyl] } zirconium dichloride; dimethylsilanediylbis 1- 2-phenyl, 4-(2-n-buty lphenyl)indeny 1] } zirconium dichloride; dimethylsilanediylbis 2-n-propyl, 4-(2-isobutylphenyl)indenyl] } zirconium dichloride; dimethylsilanediylbis 2-isopropyl, 4-(2-isobuty lphenyl)indenyl] } zirconium dichloride; dimethylsilanediylbis 1- 2-n-butyl, 4-(2-isobutylphenyl)indenyl]} zirconium dichloride; dimethylsilanediylbis 1- 2-isobutyl, 4-(2-isobutylphenyl)indenyl]} zirconium dichloride; dimethylsilanediylbis 1- 2-sec-butyl, 4-(2-isobutylphenyl)indenyl]}zirconium dichloride; dimethylsilanediylbis 1- 2-tert-butyl, 4-(2-isobutylphenyl)indenyl] } zirconium dichloride; dimethylsilanediylbis 1- 2-phenyl, 4-(2-isobutylphenyl)indenyl] } zirconium dichloride; dimethylsilanediylbis 2-n-propyl, 4-(2-sec-butylphenyl)indenyl] } zirconium dichloride; dimethylsilanediylbis 2-isopropyl, 4-(2-sec-butylphenyl)indenyl] } zirconium dichloride; dimethylsilanediylbis 2-n-butyl, 4-(2-sec-butylphenyl)indenyl]} zirconium dichloride; dimethylsilanediylbis 2-isobutyl, 4-(2-sec-buty lphenyl)indenyl] } zirconium dichloride; dimethylsilanediylbis 1- 2-sec-butyl, 4-(2-sec-butylphenyl)indenyl]}zirconium dichloride; dimethylsilanediylbis 1- 2-tert-butyl, 4-(2-sec-butylpheny l)indenyl] } zirconium dichloride; dimethylsilanediylbis 1- 2-phenyl, 4-(2-sec-butylphenyl)indenyl] } zirconium dichloride; dimethylsilanediylbis 2-n-propyl, 4-(2-tert-butylphenyl)indenyl] } zirconium dichloride; dimethylsilanediylbis 1- 2-isopropyl, 4-(2-tert-butylphenyl)indenyl]} zirconium dichloride; dimethylsilanediylbis 2-n-butyl, 4-(2-tert-butylphenyl)indenyl] } zirconium dichloride; dimethylsilanediylbis 1- 2-isobutyl, 4-(2-tert-butylphenyl)indenyl] } zirconium dichloride; dimethylsilanediylbis 1- 2-sec-butyl, 4-(2-tert-butylphenyl)indenyl] } zirconium dichloride; dimethylsilanediylbis 1- 2-tert-butyl, 4-(2-tert-butylphenyl)indenyl] } zirconium dichloride; dimethylsilanediylbis [H 2-phenyl, 4-(2-tert-buty lphenyl)indeny 1] } zirconium dichloride; dimethylsilanediylbis [H 2-n-propyl, 4-(2-biphenyl)indenyl] } zirconium dichloride; dimethylsilanediylbis i H 2-isopropyl, 4-(2-biphenyl)indeny 1] } zirconium dichloride; dimethylsilanediylbis [i-[ 2-n-butyl, 4-(2-biphenyl)indenyl]} zirconium dichloride; dimethylsilanediylbis [i-[ 2-isobutyl, 4-(2-biphenyl)indenyl]} zirconium dichloride; dimethylsilanediylbis [ i-[ 2-sec-butyl, 4-(2-biphenyl)indenyl]} zirconium dichloride; dimethylsilanediylbis [ i-[ 2-tert-butyl, 4-(2-biphenyl)indenyl] } zirconium dichloride; dimethylsilanediylbis [i-[ 2-phenyl, 4-(2-biphenyl)indenyl] } zirconium dichloride; dimethylsilanediylbis [ i-[ 2-n-propyl, 4-(2-α-naphthylphenyl)indenyl] } zirconium dichloride; dimethylsilanediylbis [H 2-isopropyl, 4-(2-α-naphthylphenyl)indeny 1] } zirconium dichloride; dimethylsilanediylbis [i-[ 2-n-butyl, 4-(2-α-naphthylphenyl)indenyl]} zirconium dichloride; dimethylsilanediylbis [i-[ 2-isobutyl, 4-(2-α-naphthylphenyl)indenyl] } zirconium dichloride; dimethylsilanediylbis [i-[ 2-sec-butyl, 4-(2-α-naphthylpheny l)indeny 1] } zirconium dichloride; dimethylsilanediylbis [H 2-tert-butyl, 4-(2-α-naphthylphenyl)indenyl] } zirconium dichloride; dimethylsilanediylbis [H 2-phenyl, 4-(2-α-naphthy lpheny l)indeny 1] } zirconium dichloride; dimethylsilanediylbis [i-[ 2-n-propyl, 4-(2-β-naphthy lpheny l)indenyl] } zirconium dichloride; dimethylsilanediylbis H 2-isopropyl, 4-(2-β-naphthylphenyl)indenyl]} zirconium dichloride; dimethylsilanediylbis 2-n-butyl, 4-(2-β-naphthylphenyl)indenyl] } zirconium dichloride; dimethylsilanediylbis 1- 2-isobutyl, 4-(2-β-naphthylphenyl)indenyl] } zirconium dichloride; dimethylsilanediylbis 2-sec-butyl, 4-(2-β-naphthy lphenyl)indeny 1] } zirconium dichloride; dimethylsilanediylbis 2-tert-butyl, 4-(2-β-naphthylphenyl)indenyl] }zirconium dichloride; dimethylsilanediylbis 2-phenyl, 4-(2-β-naphthylphenyl)indenyl] jzirconium dichloride; dimethylsilanediylbis 1- 2-n-propyl, 4-(2 -trifluoromethy lpheny l)indenyl] } - zirconium dichloride; dimethylsilanediylbis 2-isopropyl, 4-(2-trifluoromethylphenyl)indenyl] } - zirconium dichloride; dimethylsilanediylbis 2-n-butyl, 4-(2-trifluoromethy lphenyl)indenyl] } - zirconium dichloride; dimethylsilanediylbis 1- 2-isobutyl, 4-(2-trifluoromethylphenyl)indenyl] } - zirconium dichloride; dimethylsilanediylbis 2-sec-butyl, 4-(2-trifluoromethylphenyl)indenyl] } ■ zirconium dichloride; dimethylsilanediylbis 2-tert-butyl, 4-(2-trifluoromethylphenyl)indenyl] } - zirconium dichloride; dimethylsilanediylbis 2-phenyl, 4-(2-trifluoromethylphenyl)indenyl]}- zirconium dichloride; dimethylsilanediylbis 1- 2-n-propyl, 4-(2-trimethylsily lpheny l)indenyl]}- zirconium dichloride; dimethylsilanediylbis 1- 2-isopropyl, 4-(2-trimethylsilylphenyl)indenyl] } - zirconium dichloride; dimethylsilanediylbis 1- 2-n-butyl, 4-(2-trimethylsilylphenyl)indenyl] } -zirconium dichloride; dimethylsilanediylbis 1- 2-isobutyl, 4-(2-trimethylsilylphenyl)indenyl] } - zirconium dichloride; dimethylsilanediylbis 1- 2-sec-butyl, 4-(2-trimethylsilylphenyl)indenyl]}- zirconium dichloride; dimethylsilanediylbis 1- 2 -tert-butyl, 4-(2-trimethylsily lpheny l)indenyl] } - zirconium dichloride; dimethylsilanediylbis 2-phenyl, 4-(2-trimethylsilylphenyl)indeny 1] } -zirconium dichloride; dimethylsilanediylbis 1- 2-n-propyl, 4-(2,3-dimethylphenyl)indenyl]} zirconium dichloride; dimethylsilanediylbis 1- 2-isopropyl, 4-(2,3-dimethylphenyl)indenyl] }zirconium dichloride; dimethylsilanediylbis 2-n-butyl, 4-(2,3-dimethylphenyl)indenyl] } zirconium dichloride; dimethylsilanediylbis 2-isobutyl, 4-(2,3-dimethylphenyl)indenyl]}zirconium dichloride; dimethylsilanediylbis 2-sec-butyl, 4-(2,3-dimethylphenyl)indenyl] }zirconium dichloride; dimethylsilanediylbis 2-tert-butyl, 4-(2,3-dimethylphenyl)indenyl]}zirconium dichloride; dimethylsilanediylbis 1- 2-phenyl, 4-(2,3-dimethylphenyl)indenyl]}zirconium dichloride; dimethylsilanediylbis 1- 2-n-propyl, 4-(2,3,4-trimethylphenyl)indenyl]}zirconium dichloride; dimethylsilanediylbis 1- 2-isopropyl, 4-(2,3,4-trimethylphenyl)indenyl]} zirconium dichloride; dimethylsilanediylbis 1- 2-n-butyl, 4-(2,3,4-trimethylphenyl)indenyl]} zirconium dichloride; dimethylsilanediylbis 1- 2-isobutyl, 4-(2,3,4-trimethylphenyl)indenyl] }zirconium dichloride; dimethylsilanediylbis 1- 2-sec-butyl, 4-(2,3,4-trimethylphenyl)indenyl]} zirconium dichloride; dimethylsilanediylbis 2-tert-butyl, 4-(2,3,4-trimethylphenyl)indenyl]} zirconium dichloride; dimethylsilanediylbis 1- 2-phenyl, 4-(2,3,4-trimethylphenyl)indenyl]}zirconium dichloride; dimethylsilanediylbis 1- 2-n-propyl, 4-(2,3,5-trimethylphenyl)indenyl]}zirconium dichloride; dimethylsilanediylbis 1- 2-isopropyl, 4-(2,3,5-trimethylphenyl)indenyl]} zirconium dichloride; dimethylsilanediylbis 1- 2-n-butyl, 4-(2,3,5-trimethylphenyl)indenyl]}zirconium dichloride; dimethylsilanediylbis 2-isobutyl, 4-(2,3 ,5-trimethylphenyl)indenyl] } zirconium dichloride; dimethylsilanediylbis 2-sec-butyl, 4-(2,3,5-trimethylphenyl)indenyl]} zirconium dichloride; dimethylsilanediylbis 1- 2-tert-butyl, 4-(2,3,5-trimethylphenyl)indenyl]} zirconium dichloride; dimethylsilanediylbis 1- 2-phenyl, 4-(2,3,5-trimethylphenyl)indenyl]}zirconium dichloride; dimethylsilanediylbis 1- 2-n-propyl, 4-(2-methylphenyl)indenyl] } zirconium dimethyl; dimethylsilanediylbis 1- 2-isopropyl, 4-(2-methylphenyl)indenyl] } zirconium dimethyl; dimethylsilanediylbis 1- 2-n-butyl, 4-(2-methylphenyl)indenyl] } zirconium dimethyl; dimethylsilanediylbis 1- 2-isobutyl, 4-(2-methylphenyl)indenyl] } zirconium dimethyl; dimethylsilanediylbis 1- 2-sec-butyl, 4-(2-methy lpheny l)indenyl]} zirconium dimethyl; dimethylsilanediylbis 1- 2-tert-butyl, 4-(2-methy lpheny l)indeny 1] } zirconium dimethyl; dimethylsilanediylbis 1- 2-phenyl, 4-(2-methylphenyl)indenyl]} zirconium dimethyl; dimethylsilanediylbis 2-n-propyl, 4-(2-ethylphenyl)indenyl]} zirconium dimethyl; dimeth -isopropyl, 4-(2-ethylphenyl)indenyl]} zirconium dimeth dimeth -n-butyl, 4-(2-ethylphenyl)indenyl]} zirconium dimeth dimeth -isobutyl, 4-(2-ethylphenyl)indenyl] } zirconium dimeth dimeth -sec-butyl, 4-(2-ethylphenyl)indenyl] } zirconium dimeth dimeth -tert-butyl, 4-(2-ethylphenyl)indenyl] } zirconium dimeth dimeth -phenyl, 4-(2-ethylphenyl)indenyl] } zirconium dimeth dimeth -n-propyl, 4-(2-n-propy lpheny l)indenyl] } zirconium dimeth dimeth -isopropyl, 4-(2-n-propylphenyl)indenyl] } zirconium dimeth dimeth -n-butyl, 4-(2-n-propylphenyl)indenyl] } zirconium dimeth dimeth -isobutyl, 4-(2-n-propylphenyl)indenyl] } zirconium dimeth dimeth -sec-butyl, 4-(2-n-propylphenyl)indenyl] } zirconium dimeth dimeth -tert-butyl, 4-(2-n-propylphenyl)indenyl]} zirconium dimeth dimeth -phenyl, 4-(2-n-propylphenyl)indenyl] } zirconium dimeth dimeth -n-propyl, 4-(2-isopropylphenyl)indenyl] } zirconium dimeth dimeth -isopropyl, 4-(2-isopropylphenyl)indenyl]} zirconium dimeth dimeth -n-butyl, 4-(2-isopropylphenyl)indenyl] } zirconium dimeth
Figure imgf000028_0001
dimethy si lanediylbis 2-isobutyl, 4-(2-isopropylphenyl)indenyl]} zirconium dimethy dimethy si lanediylbis 2-sec-butyl, 4-(2-isopropylphenyl)indenyl]} zirconium dimethy dimethy si lanediylbis 2-tert-butyl, 4-(2-isopropylphenyl)indenyl]} zirconium dimethy dimethy si lanediylbis 2-phenyl, 4-(2-isopropylphenyl)indenyl] } zirconium dimethy dimethy si lanediylbis 2-n-propyl, 4-(2-n-butylphenyl)indenyl] } zirconium dimethy dimethy si lanediylbis 2-isopropyl, 4-(2-n-butylphenyl)indenyl]} zirconium dimethy dimethy si lanediylbis 2-n-butyl, 4-(2-n-butylphenyl)indenyl] } zirconium dimethy dimethy si lanediylbis 2-isobutyl, 4-(2-n-butylphenyl)indenyl] } zirconium dimethy dimethy si lanediylbis 2-sec-butyl, 4-(2-n-butylphenyl)indenyl] } zirconium dimethy dimethy si lanediylbis 2-tert-butyl, 4-(2-n-butylphenyl)indenyl] } zirconium dimethy dimethy si lanediylbis 2-phenyl, 4-(2-n-butylphenyl)indenyl] } zirconium dimethy dimethy SI lanediylbis 2-n-propyl, 4-(2-isobutylphenyl)indenyl] } zirconium dimethy dimethy SI lanediylbis 2-isopropyl, 4-(2-isobutylphenyl)indenyl]}zirconium dimethy dimethy SI lanediylbis 2-n-butyl, 4-(2-isobutylphenyl)indenyl]} zirconium dimethy dimethy SI lanediylbis 2-isobutyl, 4-(2-isobuty lphenyl)indenyl] } zirconium dimethy dimethy SI lanediylbis 2-sec-butyl, 4-(2-isobuty lpheny l)indenyl]} zirconium dimethy dimethy si lanediylbis 2-tert-butyl, 4-(2-isobutylphenyl)indenyl] } zirconium dimethy dimethy SI lanediylbis 2-phenyl, 4-(2-isobuty lpheny l)indenyl] } zirconium dimethy dimethy SI lanediylbis 2-n-propyl, 4-(2-sec-butylphenyl)indenyl] } zirconium dimethy dimethy SI lanediylbis 2-isopropyl, 4-(2-sec-butylphenyl)indenyl] } zirconium dimethy dimethy SI lanediylbis 2-n-butyl, 4-(2-sec-butylphenyl)indenyl]} zirconium dimethy dimethy SI lanediylbis 2-isobutyl, 4-(2-sec-butylphenyl)indenyl] } zirconium dimethy dimethy SI lanediylbis 2-sec-butyl, 4-(2-sec-butylphenyl)indenyl] } zirconium dimethy dimethy SI lanediylbis 2-tert-butyl, 4-(2-sec-buty lpheny l)indenyl] } zirconium dimethy dimethy SI lanediylbis 2-phenyl, 4-(2-sec-butylphenyl)indenyl]} zirconium dimethy dimethy SI lanediylbis 2-n-propyl, 4-(2-tert-butylphenyl)indenyl] } zirconium dimethy dimethy SI lanediylbis 2-isopropyl, 4-(2-tert-butylphenyl)indenyl] } zirconium dimethy dimethy SI lanediylbis 2-n-butyl, 4-(2-tert-butylphenyl)indenyl] } zirconium dimethy dimethy SI lanediylbis 2-isobutyl, 4-(2-tert-butylphenyl)indenyl] } zirconium dimethy dimethy SI lanediylbis 2-sec-butyl, 4-(2-tert-butylphenyl)indenyl]} zirconium dimethy dimethy SI lanediylbis 2-tert-butyl, 4-(2-tert-buty lpheny l)indeny 1] } zirconium dimethy dimethy SI lanediylbis 2-phenyl, 4-(2-tert-butylphenyl)indenyl] } zirconium dimethy dimethy si anediylbis 2-n-propyl, 4-(2-biphenyl)indenyl]} zirconium dimethyl; dimethy si anediylbis 2-isopropyl, 4-(2-biphenyl)indenyl] } zirconium dimethy dimethy si anediylbis 2-n-butyl, 4-(2-biphenyl)indenyl]} zirconium dimethyl; dimethy si anediylbis 2-isobutyl, 4-(2-biphenyl)indenyl]} zirconium dimethyl; dimethy si anediylbis 2-sec-butyl, 4-(2-biphenyl)indenyl] } zirconium dimethyl; dimethy si anediylbis 2-tert-butyl, 4-(2-biphenyl)indenyl]} zirconium dimethyl; dimethy si anediylbis 2-phenyl, 4-(2-biphenyl)indenyl]} zirconium dimethyl; dimethy SI anediylbis 2-n-propyl, 4-(2-α-naphthylphenyl)indenyl] } zirconium dimethy dimethy SI anediylbis 2-isopropyl, 4-(2-α-naphthylphenyl)indenyl] } zirconium dimethy dimethy SI anediylbis 2-n-butyl, 4-(2-α-naphthylphenyl)indenyl] } zirconium dimethy dimethy SI anediylbis 2-isobutyl, 4-(2-α-naphthy lpheny l)indeny 1] } zirconium dimethy dimethy SI anediylbis 2-sec-butyl, 4-(2-α-naphthylphenyl)indenyl]} zirconium dimethy dimethy SI anediylbis 2-tert-butyl, 4-(2-α-naphthylphenyl)indenyl] } zirconium dimethy dimethy SI anediylbis 2-phenyl, 4-(2-α-naphthylphenyl)indenyl] } zirconium dimethy dimethy SI anediylbis 2-n-propyl, 4-(2-β-naphthy lpheny l)indenyl]} zirconium dimethy dimethy SI anediylbis 2-isopropyl, 4-(2-β-naphthylphenyl)indenyl]}zirconium dimethy dimethy SI anediylbis 2-n-butyl, 4-(2-β-naphthylphenyl)indenyl]}zirconium dimethy dimethy SI anediylbis 2-isobutyl, 4-(2-β-naphthy lpheny l)indenyl] } zirconium dimethy dimethy SI anediylbis 2-sec-butyl, 4-(2-β-naphthy lpheny l)indenyl]} zirconium dimethy dimethylsilanediylbis 2-tert-butyl, 4-(2-β-naphthylphenyl)indenyl] } zirconium dimethyl; dimethylsilanediylbis 2-phenyl, 4-(2-β-naphthy lpheny l)indenyl]} zirconium dimethyl; dimethylsilanediylbis 2-n-propyl, 4-(2-trifluoromethylpheny l)indeny 1] } - zirconium dimethyl; dimethylsilanediylbis 2-isopropyl, 4-(2-trifluoromethylphenyl)indenyl] } - zirconium dimethyl; dimethylsilanediylbis 2-n-butyl, 4-(2-trifluoromethylphenyl)indenyl] }- zirconium dimethyl; dimethylsilanediylbis 2-isobutyl, 4-(2-trifluoromethylphenyl)indenyl] } - zirconium dimethyl; dimethylsilanediylbis 2-sec-butyl, 4-(2-trifluoromethylphenyl)indenyl] } - zirconium dimethyl; dimethylsilanediylbis 2-tert-butyl, 4-(2-trifluoromethylphenyl)indenyl] } - zirconium dimethyl; dimethylsilanediylbis 2-phenyl, 4-(2-trifluoromethylphenyl)indenyl] } - zirconium dimethyl; dimethylsilanediylbis 2-n-propyl, 4-(2-trimethylsilylphenyl)indenyl] } - zirconium dimethyl; dimethylsilanediylbis 2-isopropyl, 4-(2-trimethylsilylphenyl)indenyl]}- zirconium dimethyl; dimethylsilanediylbis 2-n-butyl, 4-(2-trimethylsilylphenyl)indenyl] } -zirconium dimethyl; dimethylsilanediylbis 2-isobutyl, 4-(2-trimethylsilylphenyl)indenyl] }- zirconium dimethyl; dimethylsilanediylbis 2-sec-butyl, 4-(2-trimethylsilylphenyl)indenyl] } - zirconium dimethyl; dimethylsilanediylbis 2-tert-butyl, 4-(2-trimethy lsily lphenyl)indeny 1] } - zirconium dimethyl; dimethylsilanediylbis 2-phenyl, 4-(2-trimethylsilylphenyl)indenyl] } -zirconium dimethyl; dimethyls -n-propyl, 4-(2,3-dimethylphenyl)indenyl]}zirconium dimethyl; dimethyls -isopropyl, 4-(2,3-dimethylphenyl)indenyl]} zirconium dimethyl; dimethyls -n-butyl, 4-(2,3-dimethylphenyl)indenyl] } zirconium dimethyl; dimethyls -isobutyl, 4-(2,3-dimethylphenyl)indenyl]}zirconium dimethyl dimethyls -sec-butyl, 4-(2,3-dimethylphenyl)indenyl]}zirconium dimethyl; dimethyls -tert-butyl, 4-(2,3 -dimethy lphenyl)indenyl]} zirconium dimethyl; dimethyls -phenyl, 4-(2,3-dimethylphenyl)indenyl]}zirconium dimethyl; dimethyls -n-propyl, 4-(2,3,4-trimethylphenyl)indenyl]} zirconium dimethyl; dimethyls -isopropyl, 4-(2,3,4-trimethylphenyl)indenyl] } zirconium dimethyls -n-butyl, 4-(2,3,4-trimethylphenyl)indenyl]}zirconium dimethyl; dimethyls -isobutyl, 4-(2,3,4-trimethylphenyl)indenyl]}zirconium dimethyl; dimethyls -sec-butyl, 4-(2,3,4-trimethylphenyl)indenyl]} zirconium dimethyls -tert-butyl, 4-(2,3,4-trimethylphenyl)indenyl]} zirconium dimethyls -phenyl, 4-(2, 3, 4-trimethy lpheny l)indenyl]} zirconium dimethyl; dimethyls -n-propyl, 4-(2,3,5-trimethylphenyl)indenyl]}zirconium dimethyl; dimethyls
Figure imgf000033_0001
-isopropyl, 4-(2,3,5-trimethylphenyl)indenyl]} zirconium dimethyl; dimethylsilanediylbis l-[2 -n-butyl, 4-(2, 3, 5 -trimethy lpheny l)indenyl]} zirconium dimethyl; dimethylsilanediylbis 1 - [2-isobutyl, 4-(2,3 ,5 -trimethy lphenyl)indenyl] } zirconium dimethyl; dimethylsilanediylb is l-[2-sec -butyl, 4-(2,3,5-trimethylphenyl)indenyl]} zirconium dimethyl dimethylsilanediylb I;S 1 -[2-tert-butyl, 4-(2,3,5-trimethylphenyl)indenyl] } zirconium dimethyl dimethylsilanediylbis l-[2 -phenyl, 4-(2,3,5-trimethylphenyl)indenyl]} zirconium dimethyl; dimethylsilanediylbis 1 -[2-n-propyl, 4-(2-methylphenyl)indenyl] } hafnium dichloride; dimethylsilanediylbis 1 -[2-isopropyl, 4-(2-methy lpheny l)indenyl] } hafnium dichloride; dimethylsilanediylbis 1 -[2-n-butyl, 4-(2-methylphenyl)indenyl] } hafnium dichloride; dimethylsilanediylbis 1 -[2-isobutyl, 4-(2-methylphenyl)indenyl]} hafnium dichloride; dimethylsilanediylbis 1 -[2-sec-butyl, 4-(2-methylphenyl)indenyl] }hafnium dichloride; dimethylsilanediylbis 1 -[2-tert-butyl, 4-(2-methylphenyl)indenyl] } hafnium dichloride; dimethylsilanediylbis 1 -[2-phenyl, 4-(2-methylphenyl)indenyl] } hafnium dichloride; dimethylsilanediylbis 1 -[2-n-propyl, 4-(2-ethy lpheny l)indenyl] } hafnium dichloride; dimethylsilanediylbis 1 -[2-isopropyl, 4-(2-ethylphenyl)indenyl]} hafnium dichloride; dimethylsilanediylbis 1 -[2-n-butyl, 4-(2-ethylphenyl)indenyl]} hafnium dichloride; dimethylsilanediylbis 1 -[2-isobutyl, 4-(2-ethy lpheny l)indenyl]} hafnium dichloride; dimethylsilanediylbis! 1 -[ 2-sec-butyl, 4-(2-ethylphenyl)indenyl] } hafnium dichloride; dimethylsilanediylbis! l-[ 2-tert-butyl, 4-(2-ethylphenyl)indenyl] } hafnium dichloride; dimethylsilanediylbis! 1 -[ 2-phenyl, 4-(2-ethylphenyl)indenyl]} hafnium dichloride; dimethylsilanediylbis! l-[ 2-n-propyl, 4-(2-n-propylphenyl)indenyl] } hafnium
* dichloride; dimethylsilanediylbis! l-[ 2-isopropyl, 4-(2-n-propylphenyl)indenyl] } hafnium dichloride; dimethylsilanediylbis! l-[ 2-n-butyl, 4-(2-n-propylpheny l)indenyl] } hafnium dichloride; dimethylsilanediylbis! 1 -[ 2-isobutyl, 4-(2-n-propylphenyl)indenyl] } hafnium dichloride; dimethylsilanediylbis { 1 - [ 2-sec-butyl, 4-(2-n-propylphenyl)indenyl] } hafnium dichloride; dimethylsilanediylbis! l-[ 2-tert-butyl, 4-(2-n-propylphenyl)indenyl] } hafnium dichloride; dimethylsilanediylbis! l-[ 2-phenyl, 4-(2-n-propy lpheny l)indenyl] } hafnium dichloride; dimethylsilanediylbis! l-[ 2-n-propyl, 4-(2-isopropylphenyl)indenyl] }hafnium dichloride; dimethylsilanediylbis! l-[ 2-isopropyl, 4-(2-isopropylphenyl)indenyl]}hafnium dichloride; dimethylsilanediylbis! l-[ 2-n-butyl, 4-(2-isopropylphenyl)indenyl] }hafnium dichloride; dimethylsilanediylbis! l-[ 2-isobutyl, 4-(2-isopropy lpheny l)indenyl]} hafnium dichloride; dimethylsilanediylbis! l-[ 2-sec-butyl, 4-(2-isopropylphenyl)indenyl]}hafnium dichloride; dimethylsilanediylbis! l-[. 2-tert-butyl, 4-(2-isopropylphenyl)indenyl]} hafnium dichloride; dimethylsilanediylbis 2-phenyl, 4-(2-isopropylphenyl)indenyl]} hafnium dichloride; dimethylsilanediylbis 2-n-propyl, 4-(2-n-buty lpheny l)indenyl] } hafnium dichloride; dimethylsilanediylbis 2-isopropyl, 4-(2-n-butylphenyl)indeny 1] } hafnium dichloride; dimethylsilanediylbis 2-n-butyl, 4-(2-n-butylphenyl)indenyl] } hafnium dichloride; dimethylsilanediylbis 1- 2-isobutyl, 4-(2-n-buty lpheny l)indenyl] } hafnium dichloride; dimethylsilanediylbis 1- 2-sec-butyl, 4-(2-n-butylphenyl)indenyl]} hafnium dichloride; dimethylsilanediylbis 1- 2-tert-butyl, 4-(2-n-buty lphenyl)indenyl] } hafnium dichloride; dimethylsilanediylbis 1- 2-phenyl, 4-(2-n-butylphenyl)indenyl] }hafnium dichloride; dimethylsilanediylbis 1- 2-n-propyl, 4-(2-isobutylphenyl)indenyl]} hafnium dichloride; dimethylsilanediylbis 1- 2-isopropyl, 4-(2-isobutylphenyl)indenyl] } hafnium dichloride; dimethylsilanediylbis 1- 2-n-butyl, 4-(2-isobutylphenyl)indenyl] } hafnium dichloride; dimethylsilanediylbis 1- 2-isobutyl, 4-(2-isobutylphenyl)indenyl] }hafnium dichloride; dimethylsilanediylbis 1- 2-sec-butyl, 4-(2-isobutylphenyl)indenyl]} hafnium dichloride; dimethylsilanediylbis 1- 2-tert-butyl, 4-(2-isobutylphenyl)indenyl] }hafnium dichloride; dimethylsilanediylbis 1- 2-phenyl, 4-(2-isobutylphenyl)indenyl]} hafnium dichloride; dimethylsilanediylbis 2-n-propyl, 4-(2-sec-butylphenyl)indenyl]}hafnium dichloride; dimethyls lanediylbis 2-isopropyl, 4-(2-sec-butylphenyl)indenyl] } hafnium dichloride dimethyls lanediylbis 2-n-butyl, 4-(2-sec-butylphenyl)indenyl]} hafnium dichloride dimethyls lanediylbis 2-isobutyl, 4-(2-sec-buty lpheny l)indenyl] } hafnium dichloride dimethyls lanediylbis 2-sec-butyl, 4-(2-sec-butylphenyl)indenyl]} hafnium dichloride dimethyls lanediylbis 2-tert-butyl, 4-(2-sec-butylphenyl)indenyl] }hafnium dichloride dimethyls lanediylbis 2-phenyl, 4-(2-sec-butylphenyl)indenyl] } hafnium dichloride dimethyls lanediylbis 2-n-propyl, 4-(2-tert-butylphenyl)indenyl] } hafnium dichloride dimethyls lanediylbis 2-isopropyl, 4-(2-tert-butylphenyl)indenyl] } hafnium dichloride dimethyls lanediylbis 2-n-butyl, 4-(2-tert-butylphenyl)indenyl] } hafnium dichloride dimethyls lanediylbis 2-isobutyl, 4-(2-tert-butylphenyl)indenyl] } hafnium dichloride dimethyls lanediylbis 2-sec-butyl, 4-(2-tert-butylphenyl)indenyl] }hafnium dichloride dimethyls lanediylbis 2-tert-butyl, 4-(2-tert-butylphenyl)indenyl]} hafnium dichloride dimethyls lanediylbis 2-phenyl, 4-(2-tert-butylphenyl)indenyl]} hafnium dichloride dimethyls lanediylbis 2-n-propyl, 4-(2-biphenyl)indenyl]} hafnium dichloride; dimethyls lanediylbis 2-isopropyl, 4-(2-biphenyl)indenyl]} hafnium dichloride; dimethyls lanediylbis 2-n-butyl, 4-(2-biphenyl)indenyl]} hafnium dichloride; dimethyls lanediylbis 2-isobutyl, 4-(2-biphenyl)indenyl]}hafnium dichloride; dimethyls lanediylbis 2-sec-butyl, 4-(2-biphenyl)indenyl]}hafnium dichloride; dimethyls lanediylbis 2-tert-butyl, 4-(2-biphenyl)indenyl]} hafnium dichloride; dimethylsilanediylbis (W 2-phenyl, 4-(2-biphenyl)indenyl]} hafnium dichloride; dimethylsilanediylbis* [ i-[ 2-n-propyl, 4-(2-α-naphthy lpheny l)indenyl] } hafnium dichloride; dimethylsilanediylbis! (H 2-isopropyl, 4-(2-α-naphthylphenyl)indenyl] }hafnium dichloride; dimethylsilanediylbis (H 2-n-butyl, 4-(2-α-naphthylphenyl)indenyl] }hafnium dichloride; dimethylsilanediylbis [H 2-isobutyl, 4-(2-α-naphthylphenyl)indenyl] }hafnium dichloride; dimethylsilanediylbisi [H 2-sec-butyl, 4-(2-α-naphthylphenyl)indenyl]}hafnium dichloride; dimethylsilanediylbis [ i-[ 2-tert-butyl, 4-(2-α-naphthy lpheny l)indenyl] } hafnium dichloride; dimethylsilanediylbis (H 2-phenyl, 4-(2-α-naphthylpheny l)indeny 1] } hafnium dichloride; dimethylsilanediylbis \ [H 2-n-propyl, 4-(2-β-naphthy lpheny l)indenyl]} hafnium dichloride; dimethylsilanediylbis (H 2-isopropyl, 4-(2-β-naphthylphenyl)indenyl]} hafnium dichloride; dimethylsilanediylbis (H 2-n-butyl, 4-(2-β-naphthylphenyl)indenyl] }hafnium dichloride; dimethylsilanediylbis 'XI 2-isobutyl, 4-(2-β-naphthylphenyl)indenyl]}hafnium dichloride; dimethylsilanediylbis [ i-[- 2-sec-butyl, 4-(2-β-naphthylphenyl)indenyl]} hafnium dichloride; dimethylsilanediylbis [ i-[ 2- -tert-butyl, 4-(2-β-naphthy lpheny l)indenyl]} hafnium dichloride; dimethylsilanediylbis [ i-P 2-phenyl, 4-(2-β-naphthylphenyl)indenyl] }hafnium dichloride; dimethylsilanediylbis [i- 2-n-propyl, 4-(2-trifluoromethylphenyl)indenyl]}- hafnium dichloride; dimethylsilanediylbis 1- 2-isopropyl, 4-(2-trifluoromethylphenyl)indenyl] } - hafnium dichloride; dimethylsilanediylbis 1- 2-n-butyl, 4-(2-trifluoromethylphenyl)indenyl] } - hafnium dichloride; dimethylsilanediylbis 1- 2-isobutyl, 4-(2-trifluoromethy lpheny l)indenyl] } - hafnium dichloride; dimethylsilanediylbis 1- 2-sec-butyl, 4-(2-trifluoromethylphenyl)indenyl] } - hafnium dichloride; dimethylsilanediylbis 2-tert-butyl, 4-(2-trifluoromethylphenyl)indenyl] } - hafnium dichloride; dimethylsilanediylbis 2-phenyl, 4-(2-trifluoromethy lpheny l)indenyl] } - hafnium dichloride; dimethylsilanediylbis 1- 2-n-propyl, 4-(2-trimethylsilylphenyl)indenyl] } hafnium dichloride; dimethylsilanediylbis 2-isopropyl, 4-(2 -trimethylsily lpheny l)indenyl]}- hafnium dichloride; dimethylsilanediylbis 2-n-butyl, 4-(2-trimethylsilylphenyl)indenyl] } hafnium dichloride; dimethylsilanediylbis 2-isobutyl, 4-(2-trimethylsilylphenyl)indenyl]}hafnium dichloride; dimethylsilanediylbis 2-sec-butyl, 4-(2-trimethylsilylpheny l)indeny 1] } - hafnium dichloride; dimethylsilanediylbis 1- 2-tert-butyl, 4-(2-trimethylsilylphenyl)indenyl]}- hafnium dichloride; dimethylsilanediylbis 1- 2 -phenyl, 4-(2-trimethylsilylphenyl)indenyl]} hafnium dichloride; dimethylsilanediylbis 1- 2-n-propyl, 4-(2,3-dimethylphenyl)indenyl]}hafnium dichloride; dimethylsilanediylbis 1- 2-isopropyl, 4-(2,3-dimethylphenyl)indenyl]}hafnium dichloride; dimethylsilanediylbis 1- 2-n-butyl, 4-(2,3-dimethylphenyl)indenyl]} hafnium dichloride; dimethyl silanediy lbi s 2-isobutyl, 4-(2,3-dimethylphenyl)indenyl] }hafnium dichloride; dimethylsilanediylbis 2-sec-butyl, 4-(2,3 -dimethy lphenyl)indenyl] } hafnium dichloride; dimethylsilanediylbis 2-tert-butyl, 4-(2,3-dimethylphenyl)indenyl]}hafnium dichloride; dimethylsilanediylbis 2-phenyl, 4-(2,3 -dimethy lphenyl)indeny 1] } hafnium dichloride; dimethylsilanediylbis 1- 2-n-propyl, 4-(2,3,4-trimethylphenyl)indenyl]}hafnium dichloride; dimethylsilanediylbis 1- 2-isopropyl, 4-(2,3,4-trimethylphenyl)indenyl]}hafnium dichloride; dimethylsilanediylbis 1- 2-n-butyl, 4-(2,3,4-trimethylphenyl)indenyl]}hafnium dichloride; dimethylsilanediylbis 2-isobutyl, 4-(2,3,4-trimethylphenyl)indenyl] hafnium dichloride; dimethylsilanediylbis 2-sec-butyl, 4-(2,3,4-trimethylphenyl)indenyl]} hafnium dichloride; dimethylsilanediylbis 2-tert-butyl, 4-(2,3 ,4-trimethylphenyl)indenyl] } hafnium dichloride; dimethylsilanediylbis 2-phenyl, 4-(2,3,4-trimethylphenyl)indenyl]}hafnium dichloride; dimethylsilanediylbis 2-n-propyl, 4-(2,3,5-trimethylphenyl)indenyl]}hafnium dichloride; dimethylsilanediylbis 2-isopropyl, 4-(2,3,5-trimethylphenyl)indenyl]}hafnium dichloride; dimethylsilanediylbis 2-n-butyl, 4-(2,3,5-trimethylphenyl)indenyl]}hafnium dichloride; dimethylsilanediylbis 2-isobutyl, 4-(2,3,5-trimethylphenyl)indenyl]} hafnium dichloride; dimethylsilanediylbis 1- 2-sec-butyl, 4-(2,3 ,5 -trimethy lphenyl)indenyl] } hafnium dichloride; dimethylsilanediylbis! l-[ 2-tert-butyl, 4-(2,3,5-trimethylphenyl)indenyl]} hafnium dichloride; dimethylsilanediylbis! \-[. 2-phenyl, 4-(2,3,5-trimethylphenyl)indenyl] }hafnium dichloride; dimethylsilanediylbis! \-[. 2-n-propyl, 4-(2-methy lpheny l)indenyl] } hafnium dimethyl; dimethylsilanediylbis! l-[. 2-isopropyl, 4-(2-methylphenyl)indenyl]} hafnium dimethyl; dimethylsilanediylbis! l-[. 2-n-butyl, 4-(2-methy lpheny l)indeny 1] } hafnium dimethyl; dimethylsilanediylbis! l-[ 2-isobutyl, 4-(2-methylphenyl)indenyl] } hafnium dimethyl; dimethylsilanediylbis! 1 -[ 2-sec-butyl, 4-(2-methylphenyl)indenyl] } hafnium dimethyl; dimethylsilanediylbis! l-[. 2-tert-butyl, 4-(2-methylphenyl)indenyl] }hafnium dimethyl; dimethylsilanediylbis! l-[ 2-phenyl, 4-(2-methy lpheny l)indeny 1] } hafnium dimethyl; dimethylsilanediylbis! l-[ 2-n-propyl, 4-(2-ethylphenyl)indenyl] } hafnium dimethyl; dimethylsilanediylbis! l-[ 2-isopropyl, 4-(2 -ethy lpheny l)indenyl] } hafnium dimethyl; dimethylsilanediylbis! 1 -[ 2-n-butyl, 4-(2-ethylphenyl)indenyl] } hafnium dimethyl; dimethylsilanediylbis! l-[ 2-isobutyl, 4-(2-ethylphenyl)indenyl]} hafnium dimethyl; dimethylsilanediylbis! 1 -[ 2-sec-butyl, 4-(2-ethylphenyl)indenyl] }hafnium dimethyl; dimethylsilanediylbis! 1 -[ 2-tert-butyl, 4-(2-ethylphenyl)indenyl]} hafnium dimethyl; dimethylsilanediylbis! l-[ 2-phenyl, 4-(2-ethy lpheny l)indenyl]} hafnium dimethyl; dimethylsilanediylbis! l-[ 2-n-propyl, 4-(2-n-propylphenyl)indenyl] } hafnium dimethyl; dimethy si lanediylbis 2-isopropyl, 4-(2-n-propy lpheny l)indenyl] } hafnium dimethy dimethy si lanediylbis 2-n-butyl, 4-(2-n-propylphenyl)indenyl] }hafnium dimethy dimethy SI lanediylbis 2-isobutyl, 4-(2-n-propylphenyl)indenyl] } hafnium dimethy dimethy SI lanediylbis 2-sec-butyl, 4-(2 -n-propy lpheny l)indenyl] } hafnium dimethy dimethy SI lanediylbis 2-tert-butyl, 4-(2-n-propy lpheny l)indenyl] } hafnium dimethy dimethy SI lanediylbis 2-phenyl, 4-(2 -n-propy lphenyl)indeny 1] } hafnium dimethy dimethy SI lanediylbis 2-n-propyl, 4-(2-isopropy lpheny l)indenyl] } hafnium dimethy dimethy SI lanediylbis 2-isopropyl, 4-(2-isopropylphenyl)indeny 1] } hafnium dimethy dimethy SI lanediylbis 2-n-butyl, 4-(2-isopropylphenyl)indenyl] } hafnium dimethy dimethy SI lanediylbis 2-isobutyl, 4-(2-isopropylphenyl)indenyl] }hafnium dimethy dimethy SI lanediylbis 2-sec-butyl, 4-(2-isopropylphenyl)indenyl]}hafnium dimethy dimethy SI lanediylbis 2-tert-butyl, 4-(2-isopropylphenyl)indenyl] }hafnium dimethy dimethy SI lanediylbis 2-phenyl, 4-(2-isopropylphenyl)indenyl]} hafnium dimethy dimethy SI lanediylbis 2-n-propyl, 4-(2-n-butylphenyl)indenyl] } hafnium dimethy dimethy SI lanediylbis 2-isopropyl, 4-(2-n-butylphenyl)indenyl] } hafnium dimethy dimethy SI lanediylbis 2-n-butyl, 4-(2-n-butylphenyl)indenyl]} hafnium dimethy dimethy si lanediylbis 2-isobutyl, 4-(2-n-butylphenyl)indenyl] }hafnium dimethy dimethy si lanediylbis 2-sec-butyl, 4-(2-n-butylphenyl)indenyl]} hafnium dimethy dimethy si lanediylbis 2-tert-butyl, 4-(2-n-buty lphenyl)indeny 1] } hafnium dimethy dimethy SI lanediylbis 2-phenyl, 4-(2-n-butylphenyl)indenyl] } hafnium dimethy dimethy SI lanediylbis 2-n-propyl, 4-(2-isobutylphenyl)indeny 1] } hafnium dimethy dimethy SI lanediylbis 2-isopropyl, 4-(2-isobutylphenyl)indenyl] }hafnium dimethy dimethy SI lanediylbis 2-n-butyl, 4-(2-isobutylphenyl)indenyl]}hafnium dimethy dimethy SI lanediylbis 2-isobutyl, 4-(2-isobutylphenyl)indenyl]} hafnium dimethy dimethy SI lanediylbis 2-sec-butyl, 4-(2-isobutylphenyl)indenyl] hafnium dimethy dimethy SI lanediylbis 2-tert-butyl, 4-(2-isobutylphenyl)indenyl] }hafnium dimethy dimethy SI lanediylbis 2-phenyl, 4-(2-isobutylphenyl)indenyl] }hafnium dimethy dimethy SI lanediylbis 2-n-propyl, 4-(2-sec-butylphenyl)indenyl]} hafnium dimethy dimethy SI lanediylbis 2-isopropyl, 4-(2-sec-butylphenyl)indenyl]}hafnium dimethy dimethy SI lanediylbis 2-n-butyl, 4-(2-sec-butylphenyl)indenyl]} hafnium dimethy dimethy SI lanediylbis 2-isobutyl, 4-(2-sec-butylphenyl)indenyl]} hafnium dimethy dimethy SI lanediylbis 2-sec-butyl, 4-(2-sec-buty lpheny l)indenyl]} hafnium dimethy dimethy si anediylbis 2-tert-butyl, 4-(2-sec-butylphenyl)indenyl] } hafnium dimethy dimethy si anediylbis 2-phenyl, 4-(2-sec-butylphenyl)indenyl] } hafnium dimethy dimethy si anediylbis 2-n-propyl, 4-(2-tert-buty lphenyl)indenyl] } hafnium dimethy dimethy si anediylbis 2-isopropyl, 4-(2-tert-butylphenyl)indenyl] } hafnium dimethy dimethy si anediylbis 2-n-butyl, 4-(2 -tert-buty lpheny l)indenyl] } hafnium dimethy dimethy si anediylbis 2-isobutyl, 4-(2-tert-butylphenyl)indenyl] } hafnium dimethy dimethy si anediylbis 2-sec-butyl, 4-(2 -tert-buty lpheny l)indeny 1] } hafnium dimethy dimethy SI anediylbis 2-tert-butyl, 4-(2 -tert-buty lphenyl)indenyl] } hafnium dimethy dimethy SI anediylbis 2-phenyl, 4-(2-tert-butylphenyl)indenyl] } hafnium dimethy dimethy anediylbis 2-n-propyl, 4-(2-biphenyl)indenyl]} hafnium dimethyl; dimethy anediylbis 2-isopropyl, 4-(2-biphenyl)indenyl]}hafnium dimethyl; dimethy anediylbis 2-n-butyl, 4-(2-biphenyl)indenyl]} hafnium dimethyl; dimethy anediylbis 2-isobutyl, 4-(2-biphenyl)indenyl]} hafnium dimethyl; dimethy anediylbis 2-sec-butyl, 4-(2-biphenyl)indenyl]}hafnium dimethyl; dimethy anediylbis 2-tert-butyl, 4-(2-biphenyl)indenyl]} hafnium dimethyl; dimethy anediylbis 2-phenyl, 4-(2-biphenyl)indenyl]} hafnium dimethyl; dimethy anediylbis 2-n-propyl, 4-(2-α-naphthylphenyl)indenyl] }hafnium dimethy dimethy SI anediylbis 2-isopropyl, 4-(2-α-naphthy lpheny l)indenyl]} hafnium dimethy dimethy SI anediylbis 2-n-butyl, 4-(2-α-naphthylphenyl)indenyl]} hafnium dimethy dimethylsilanediylbis 1- 2-isobutyl, 4-(2-α-naphthy lpheny l)indenyl] } hafnium dimethyl; dimethylsilanediylbis 2-sec-butyl, 4-(2-α-naphthylphenyl)indenyl] }hafnium dimethyl; dimethylsilanediylbis 2-tert-butyl, 4-(2-α-naphthy lpheny l)indeny 1] } hafnium dimethyl; dimethylsilanediylbis 2-phenyl, 4-(2-α-naphthylphenyl)indenyl] } hafnium dimethyl; dimethylsilanediylbis 2-n-propyl, 4-(2-β-naphthylphenyl)indenyl] }hafnium dimethyl; dimethylsilanediylbis 2-isopropyl, 4-(2-β-naphthylphenyl)indenyl] } hafnium dimethyl; dimethylsilanediylbis 1- 2-n-butyl, 4-(2-β-naphthylphenyl)indenyl] }hafnium dimethyl; dimethylsilanediylbis 2-isobutyl, 4-(2-β-naphthylphenyl)indenyl] }hafnium dimethyl; dimethylsilanediylbis 2-sec-butyl, 4-(2-β-naphthylphenyl)indenyl] }hafnium dimethyl; dimethylsilanediylbis 2-tert-butyl, 4-(2-β-naphthylphenyl)indenyl] } hafnium dimethyl; dimethylsilanediylbis 1- 2-phenyl, 4-(2-β-naphthy lpheny l)indenyl] } hafnium dimethyl; dimethylsilanediylbis 2-n-propyl, 4-(2-trifluoromethylphenyl)indenyl]}- hafnium dimethyl; dimethylsilanediylbis 2-isopropyl, 4-(2-trifluoromethylphenyl)indenyl] } - hafnium dimethyl; dimethylsilanediylbis 1- 2-n-butyl, 4-(2 -trifluoromethy lpheny l)indenyl]}- hafnium dimethyl; dimethylsilanediylbis 1- 2-isobutyl, 4-(2-trifluoromethylphenyl)indenyl] } - hafnium dimethyl; dimethylsilanediylbis 2-sec-butyl, 4-(2-trifluoromethylphenyl)indenyl] } ■ hafnium dimethyl; dimethylsilanediylbis 2-tert-butyl, 4-(2-trifluoromethylphenyl)indenyl] } - hafnium dimethyl; dimethylsilanediylbis 2-phenyl, 4-(2-trifluoromethylphenyl)indenyl]}- hafnium dimethyl; dimethylsilanediylbis 2-n-propyl, 4-(2-trimethylsilylphenyl)indenyl] } hafnium dimethyl; dimethylsilanediylbis 2-isopropyl, 4-(2-trimethylsilylphenyl)indenyl] } hafnium dimethyl; dimethylsilanediylbis 1- 2-n-butyl, 4-(2-trimethylsilylphenyl)indenyl] } hafnium dimethyl; dimethylsilanediylbis 1- 2-isobutyl, 4-(2-trimethylsilylphenyl)indenyl] } hafnium dimethyl; dimethylsilanediylbis 1- 2-sec-butyl, 4-(2-trimethylsilylphenyl)indenyl]}hafnium dimethyl; dimethylsilanediylbis 1- 2-tert-butyl, 4-(2-trimethylsilylphenyl)indenyl]} hafnium dimethyl; dimethylsilanediylbis 1- 2-phenyl, 4-(2-trimethylsilylphenyl)indenyl] }hafnium dimethyl; dimethylsilanediylbis 1- 2-n-propyl, 4-(2,3-dimethylphenyl)indenyl] }hafnium dimethyl; dimethylsilanediylbis 1- 2-isopropyl, 4-(2,3-dimethylphenyl)indenyl]}hafnium dimethyl; dimethylsilanediylbis 1- 2-n-butyl, 4-(2,3-dimethylphenyl)indenyl] }hafnium dimethyl; dimethylsilanediylbis 2-isobutyl, 4-(2,3-dimethylphenyl)indenyl]}hafnium dimethyl; dimethylsilanediylbis 1- 2-sec-butyl, 4-(2,3-dimethylphenyl)indenyl]}hafnium dimethyl; dimethylsilanediylbis 2-tert-butyl, 4-(2,3-dimethylphenyl)indenyl]}hafnium dimethyl; dimethylsilanediylbis 1- 2-phenyl, 4-(2,3-dimethylphenyl)indenyl]}hafnium dimethyl; dimethylsilanediylbis 2-n-propyl, 4-(2,3,4-trimethylphenyl)indenyl]}hafnium dimethyl; dimethylsilanediylbis 2-isopropyl, 4-(2,3,4-trimethylphenyl)indenyl]}hafnium dimethyl; dimethylsilanediylbis 2-n-butyl, 4-(2,3,4-trimethylphenyl)indenyl]}hafnium dimethyl; dimethylsilanediylbis 2-isobutyl, 4-(2,3, 4-trimethy lpheny l)indenyl]} hafnium dimethyl; dimethylsilanediylbis 1- 2-sec-butyl, 4-(2,3, 4-trimethy lpheny l)indenyl] } hafnium dimethyl; dimethylsilanediylbis 1- 2-tert-butyl, 4-(2,3,4-trimethylphenyl)indenyl] } hafnium dimethyl; dimethylsilanediylbis 1- 2-phenyl, 4-(2,3, 4-trimethy lphenyl)indeny 1] } hafnium dimethyl; dimethylsilanediylbis 1- 2-n-propyl, 4-(2,3,5-trimethylphenyl)indenyl]}hafnium dimethyl; dimethylsilanediylbis 1- 2-isopropyl, 4-(2,3,5-trimethylphenyl)indenyl]}hafnium dimethyl; dimethylsilanediylbis 1- 2-n-butyl, 4-(2,3,5-trimethylphenyl)indenyl] }hafnium dimethyl; dimethylsilanediylbis 1- 2-isobutyl, 4-(2,3,5-trimethylphenyl)indenyl] }hafnium dimethyl; dimethylsilanediylbis 1- 2-sec-butyl, 4-(2,3,5-trimethylphenyl)indenyl]} hafnium dimethyl; dimethylsilanediylbis 2-tert-butyl, 4-(2,3,5-trimethylphenyl)indenyl]} hafnium dimethyl; dimethylsilanediylbis 2-phenyl, 4-(2,3,5-trimethylphenyl)indenyl]}hafnium dimethyl;
9-silafluorendiylbis {l-[2-methyl, 4-(2-methylphenyl)indenyl]} zirconium dichloride;
9-silafluorendiylbis { 1 -[2-ethyl, 4-(2 -methy lpheny l)indenyl]} zirconium dichloride; 9-silafluorendiylbis H 2-n-propyl, 4-(2-methy lpheny l)indenyl] } zirconium dichloride;
9-silafluorendiylbis H 2-isopropyl, 4-(2-methylphenyl)indenyl] } zirconium dichloride;
9-silafluorendiylbis ι-[ 2-n-butyl, 4-(2-methylphenyl)indenyl] } zirconium dichloride;
9-silafluorendiylbis H 2-isobutyl, 4-(2-methylphenyl)indenyl] } zirconium dichloride;
9-silafluorendiylbis M 2-sec-butyl, 4-(2-methylphenyl)indenyl]} zirconium dichloride;
9-silafluorendiylbis rH 2-tert-butyl, 4-(2-methylphenyl)indenyl] } zirconium dichloride;
9-silafluorendiylbis [H 2-phenyl, 4-(2-methylphenyl)indenyl] } zirconium dichloride;
9-silafluorendiylbis [H 2-methyl, 4-(2-ethylphenyl)indenyl]} zirconium dichloride;
9-silafluorendiylbis [H 2-ethyl, 4-(2-ethylphenyl)indenyl]} zirconium dichloride;
9-silafluorendiylbis [H 2-n-propyl, 4-(2-ethylphenyl)indenyl]} zirconium dichloride;
9-silafluorendiylbis [H 2-isopropyl, 4-(2-ethylphenyl)indenyl] } zirconium dichloride;
9-silafluorendiylbis [H 2-n-butyl, 4-(2-ethylphenyl)indenyl]} zirconium dichloride;
9-silafluorendiylbis [H 2-isobutyl, 4-(2-ethylphenyl)indenyl] } zirconium dichloride;
9-silafluorendiylbis [ i-[ 2-sec-butyl, 4-(2-ethylphenyl)indenyl]} zirconium dichloride;
9-silafluorendiylbis [H 2-tert-butyl, 4-(2-ethy lpheny l)indenyl] } zirconium dichloride;
9-silafluorendiylbis E H 2-phenyl, 4-(2-ethylphenyl)indenyl]} zirconium dichloride;
9-silafluorendiylbis [ i-[ 2-methyl, 4-(2-n-propylphenyl)indenyl]} zirconium dichloride; 9-silafluorendiylbis 2-ethy 1, 4-(2-n-propylpheny l)indenyl] } zirconium dichloride;
9-silafluorendiylbis 2-n-propyl, 4-(2-n-propylphenyl)indenyl] } zirconium dichloride;
9-silafluorendiylbis 2-isopropyl, 4-(2-n-propylphenyl)indenyl] } zirconium dichloride;
9-silafluorendiylbis 1- 2-n-butyl, 4-(2-n-propy lpheny l)indeny 1] } zirconium dichloride;
9-silafluorendiylbis 2-isobutyl, 4-(2-n-propylphenyl)indenyl]} zirconium dichloride;
9-silafluorendiylbis 1- 2-sec-butyl, 4-(2-n-propylphenyl)indenyl]} zirconium dichloride;
9-silafluorendiylbis 1- 2-tert-butyl, 4-(2-n-propylphenyl)indenyl] } zirconium dichloride;
9-silafluorendiylbis 1- 2-phenyl, 4-(2-n-propylphenyl)indenyl] } zirconium dichloride;
9-silafluorendiylbis 2-methyl, 4-(2-isopropylphenyl)indenyl] } zirconium dichloride;
9-silafluorendiylbis 1- 2-ethyl, 4-(2-isopropylphenyl)indeny 1] } zirconium dichloride;
9-silafluorendiylbis 1- 2-n-propyl, 4-(2-isopropylphenyl)indenyl] } zirconium dichloride;
9-silafluorendiylbis 1- 2-isopropyl, 4-(2-isopropylphenyl)indenyl] } zirconium dichloride;
9-silafluorendiylbis 1- 2-n-butyl, 4-(2-isopropylphenyl)indenyl] } zirconium dichloride;
9-silafluorendiylbis 1- 2-isobutyl, 4-(2-isopropylphenyl)indenyl] } zirconium dichloride;
9-silafluorendiylbis 2-sec-butyl, 4-(2-isopropylphenyl)indenyl]} zirconium dichloride;
9-silafluorendiylbis 2-tert-butyl, 4-(2-isopropylphenyl)indenyl]} zirconium dichloride; 9-silafluorendiylbis 2-phenyl, 4-(2-isopropylphenyl)indenyl] } zirconium dichloride;
9-silafluorendiylbis 2-methyl, 4-(2-n-butylphenyl)indenyl] } zirconium dichloride; 9-silafluorendiylbis 2-ethyl, 4-(2 -n-buty lpheny l)indenyl] } zirconium dichloride;
9-silafluorendiylbis 2-n-propyl, 4-(2-n-butylphenyl)indenyl] } zirconium dichloride;
9-silafluorendiylbis 2-isopropyl, 4-(2-n-butylphenyl)indenyl] } zirconium dichloride;
9-silafluorendiylbis 2-n-butyl, 4-(2-n-butylphenyl)indenyl] } zirconium dichloride;
9-silafluorendiylbis 2-isobutyl, 4-(2-n-buty lpheny l)indenyl] } zirconium dichloride; 9-silafluorendiylbis 2-sec-butyl, 4-(2-n-butylphenyl)indenyl] } zirconium dichloride;
9-silafluorendiylbis 2-tert-butyl, 4-(2-n-butylphenyl)indenyl] } zirconium dichloride;
9-silafluorendiylbis 2-phenyl, 4-(2-n-butylphenyl)indenyl] } zirconium dichloride;
9-silafluorendiylbis 2-methyl, 4-(2-isobutylphenyl)indenyl] jzirconium dichloride;
9-silafluorendiylbis 2-ethyl, 4-(2-isobutylphenyl)indenyl] } zirconium dichloride; 9-silafluorendiylbis 2-n-propyl, 4-(2-isobuty lpheny l)indenyl]} zirconium dichloride;
9-silafluorendiylbis 2-isopropyl, 4-(2-isobutylphenyl)indenyl] } zirconium dichloride;
9-silafluorendiylbis 2-n-butyl, 4-(2-isobutylphenyl)indenyl] } zirconium dichloride;
9-silafluorendiylbis 2-isobutyl, 4-(2-isobutylphenyl)indenyl] } zirconium dichloride; 9-silafluorendiylbis 2-sec-butyl, 4-(2-isobutylphenyl)indenyl]} zirconium dichloride;
9-silafluorendiylbis 2-tert-butyl, 4-(2-isobuty lpheny l)indenyl]} zirconium dichloride; 9-silafluorendiylbis 2-phenyl, 4-(2-isobutylphenyl)indenyl]} zirconium dichloride;
9-silafluorendiylbis 2-methyl, 4-(2-sec-butylphenyl)indenyl] } zirconium dichloride;
9-silafluorendiylbis 2-ethyl, 4-(2-sec-butylphenyl)indenyl] } zirconium dichloride;
9-silafluorendiylbis 2-n-propyl, 4-(2-sec-butylphenyl)indenyl] } zirconium dichloride;
9-silafluorendiylbis 2-isopropyl, 4-(2-sec-buty lphenyl)indenyl] } zirconium dichloride; 9-silafluorendiylbis 2-n-butyl, 4-(2-sec-buty lpheny l)indeny 1] } zirconium dichloride;
9-silafluorendiylbis 2-isobutyl, 4-(2-sec-butylphenyl)indenyl] } zirconium dichloride;
9-silafluorendiylbis 2-sec-butyl, 4-(2-sec-buty lpheny l)indenyl] } zirconium dichloride;
9-silafluorendiylbis 2-tert-butyl, 4-(2-sec-butylphenyl)indenyl] } zirconium dichloride;
9-silafluorendiylbis 2-phenyl, 4-(2-sec-butylphenyl)indenyl] } zirconium dichloride; 9-silafluorendiylbis 2-methyl, 4-(2-tert-butylphenyl)indenyl] } zirconium dichloride;
9-silafluorendiylbis 2-ethyl, 4-(2-tert-butylphenyl)indenyl]}zirconium dichloride;
9-silafluorendiylbis 2-n-propyl, 4-(2-tert-butylphenyl)indenyl] } zirconium dichloride;
9-silafluorendiylbis 2-isopropyl, 4-(2-tert-buty lphenyl)indeny 1] } zirconium dichloride; 9-silafluorendiylbis ! 2-n-butyl, 4-(2-tert-butylphenyl)indenyl] } zirconium dichloride;
9-silafluorendiylbis{ 2-isobutyl, 4-(2-tert-butylphenyl)indenyl] } zirconium dichloride;
9-silafluorendiylbis ! 2-sec-butyl, 4-(2 -tert-buty lpheny l)indenyl] } zirconium dichloride;
9-silafluorendiylbis { 2-tert-butyl, 4-(2-tert-butylphenyl)indenyl] } zirconium dichloride;
9-silafluorendiylbis { 2-phenyl, 4-(2-tert-butylphenyl)indenyl] } zirconium dichloride;
9-silafluorendiylbis { 2-methyl, 4-(2-biphenyl)indenyl]} zirconium dichloride;
9-silafluorendiylbis! 2-ethyl, 4-(2-biphenyl)indenyl] } zirconium dichloride;
9-silafluorendiylbis! 2-n-propyl, 4-(2-biphenyl)indenyl]} zirconium dichloride;
9-silafluorendiylbis { 2-isopropyl, 4-(2-biphenyl)indenyl]} zirconium dichloride;
9-silafluorendiylbis { 2-n-butyl, 4-(2-biphenyl)indenyl]} zirconium dichloride;
9-silafluorendiylbis{ 2-isobutyl, 4-(2-biphenyl)indenyl]}zirconium dichloride;
9-silafluorendiylbis { 2-sec-butyl, 4-(2-biphenyl)indenyl]} zirconium dichloride;
9-silafluorendiylbis { 2-tert-butyl, 4-(2-biphenyl)indenyl]} zirconium dichloride;
9-silafluorendiy Ibis { 2-phenyl, 4-(2-biphenyl)indenyl]} zirconium dichloride;
9-silafluorendiy Ibis { 2-n-propyl, 4-(2-α-naphthylpheny l)indeny 1] } zirconium dichloride;
9-silafluorendiy Ibis { 2-isopropyl, 4-(2-α-naphthylphenyl)indenyl]} zirconium dichloride;
9-silafluorendiylbis ! 2-n-butyl, 4-(2-α-naphthylphenyl)indenyl] } zirconium dichloride;
9-silafluorendiylbis{ 2-isobutyl, 4-(2-α-naphthylphenyl)indenyl]} zirconium dichloride;
9-silafluorendiylbis! 2-sec-butyl, 4-(2-α-naphthy lpheny l)indenyl]} zirconium dichloride;
9-silafluorendiylbis { 2-tert-butyl, 4-(2-α-naphthy lpheny l)indenyl]} zirconium dichloride; 9-silafluorendiylbis 2-phenyl, 4-(2-α-naphthylphenyl)indenyl]} zirconium dichloride;
9-silafluorendiylbis 2-n-propyl, 4-(2-β-naphthylphenyl)indenyl] } zirconium dichloride;
9-silafluorendiylbis 2-isopropyl, 4-(2-β-naphthylphenyl)indenyl]} zirconium dichloride;
9-silafluorendiylbis 2-n-butyl, 4-(2-β-naphthylphenyl)indenyl]} zirconium dichloride;
9-silafluorendiylbis 2-isobutyl, 4-(2-β-naphthylphenyl)indenyl]} zirconium dichloride;
9-silafluorendiylbis 2-sec-butyl, 4-(2-β-naphthy lpheny l)indeny 1] } zirconium dichloride;
9-silafluorendiylbis 2-tert-butyl, 4-(2-β-naphthy lpheny l)indeny 1] } zirconium dichloride;
9-silafluorendiylbis 2-phenyl, 4-(2-β-naphthylphenyl)indenyl] } zirconium dichloride;
9-silafluorendiylbis 2-methyl, 4-(2-trifluoromethylphenyl)indenyl]} zirconium dichloride;
9-silafluorendiylbis 2-ethyl, 4-(2-trifluoromethylphenyl)indenyl]} zirconium dichloride;
9-silafluorendiylbis 2-n-propyl, 4-(2-trifluoromethylphenyl)indenyl] } - zirconium dichloride
9-silafluorendiylbis 2-isopropyl, 4-(2-trifluoromethylphenyl)indenyl] } - zirconium dichloride
9-silafluorendiylbis 2-n-butyl, 4-(2-trifluoromethylphenyl)indenyl] } -zirconium dichloride;
9-silafluorendiylbis 2-isobutyl, 4-(2-trifluoromethylphenyl)indenyl] } - zirconium dichloride
9-silafluorendiylbis 2-sec-butyl, 4-(2-trifluoromethylphenyl)indenyl] } - zirconium dichloride
9-silafluorendiylbis 2-tert-butyl, 4-(2-trifluoromethylphenyl)indenyl] } - zirconium dichloride; 9-silafluorendiylbis 2-phenyl, 4-(2-trifluoromethylphenyl)indenyl] } -zirconium dichloride;
9-silafluorendiylbis 2-methyl, 4-(2-trimethylsilylphenyl)indenyl] } zirconium dichloride; 9-silafluorendiylbis 2-ethyl, 4-(2-trimethylsilylphenyl)indenyl] } zirconium dichloride;
9-silafluorendiylbis 2-n-propyl, 4-(2-trimethylsilylphenyl)indenyl] } -zirconium dichloride;
9-silafluorendiylbis 2-isopropyl, 4-(2-trimethylsilylphenyl)indenyl]}- zirconium dichloride
9-silafluorendiylbis 2-n-butyl, 4-(2-trimethylsilylphenyl)indenyl] } -zirconium dichloride;
9-silafluorendiylbis 2-isobutyl, 4-(2-trimethylsilylphenyl)indenyl]} -zirconium dichloride; 9-silafluorendiylbis 2-sec-butyl, 4-(2-trimethylsilylphenyl)indenyl]} -zirconium dichloride;
9-silafluorendiylbis 2-tert-butyl, 4-(2-trimethylsilylphenyl)indenyl] }- zirconium dichloride
9-silafluorendiylbis 2-phenyl, 4-(2-trimethylsilylphenyl)indenyl]} -zirconium dichloride;
9-silafluorendiylbis 2-n-propyl, 4-(2,3-dimethylphenyl)indenyl] }zirconium dichloride;
9-silafluorendiylbis 2-isopropyl, 4-(2,3-dimethylphenyl)indenyl]}zirconium dichloride; 9-silafluorendiylbis 2-n-butyl, 4-(2,3-dimethylphenyl)indenyl]}zirconium dichloride;
9-silafluorendiylbis 2-isobutyl, 4-(2,3-dimethylphenyl)indenyl]}zirconium dichloride;
9-silafluorendiylbis 2-sec-butyl, 4-(2,3-dimethylphenyl)indenyl]}zirconium dichloride;
9-silafluorendiylbis 2-tert-butyl, 4-(2,3-dimethylphenyl)indenyl]} zirconium dichloride; 9-silafluorendiylbis 2-phenyl, 4-(2,3 -dimethy lpheny l)indeny 1] } zirconium dichloride;
9-silafluorendiylbis 2-n-propyl, 4-(2,3,4-trimethylphenyl)indenyl]}zirconium dichloride;
9-silafluorendiylbis 2-isopropyl, 4-(2,3,4-trimethylphenyl)indenyl]} zirconium dichloride;
9-silafluorendiylbis 2-n-butyl, 4-(2,3,4-trimethylphenyl)indenyl]} zirconium dichloride;
9-silafluorendiylbis 2-isobutyl, 4-(2,3,4-trimethylphenyl)indenyl] } zirconium dichloride;
9-silafluorendiylbis 2-sec-butyl, 4-(2,3,4-trimethylphenyl)indenyl] } zirconium dichloride
9-silafluorendiylbis 2-tert-butyl, 4-(2,3 ,4-trimethylphenyl)indeny 1] } zirconium dichloride
9-silafluorendiylbis 2-phenyl, 4-(2,3,4-trimethylphenyl)indenyl]}zirconium dichloride;
9-silafluorendiylbis 2-n-propyl, 4-(2,3,5-trimethylphenyl)indenyl]}zirconium dichloride;
9-silafluorendiylbis 2-isopropyl, 4-(2,3,5-trimethylphenyl)indenyl]} zirconium dichloride;
9-silafluorendiylbis 2-n-butyl, 4-(2,3,5-trimethylphenyl)indenyl] } zirconium dichloride;
9-silafluorendiylbis 2-isobutyl, 4-(2,3,5-trimethylphenyl)indenyl]}zirconium dichloride;
9-silafluorendiylbis 2-sec-butyl, 4-(2,3,5-trimethylphenyl)indenyl]} zirconium dichloride
9-silafluorendiylbis 2-tert-butyl, 4-(2,3,5-trimethylphenyl)indenyl]} zirconium dichloride
9-silafluorendiylbis 2-phenyl, 4-(2,3,5-trimethylphenyl)indenyl]}zirconium dichloride;
9-silafluorendiylbis! 1 - 2-n-propyl, 4-(2-methylphenyl)indenyl]}zirconium dimethyl; 9-silafluorendiylbis { 1 -[ 2. -isopropyl, 4-(2-methylphenyl)indenyl] } zirconium dimethyl;
9-silafluorendiylbis { 1 -[ 2-n-butyl, 4-(2-methylphenyl)indenyl] } zirconium dimethyl;
9-silafluorendiylbis { l-[ 2-isobutyl, 4-(2-methylphenyl)indenyl] } zirconium dimethyl;
9-silafluorendiylbis! 1 -[ 2-sec-butyl, 4-(2-methylphenyl)indenyl] } zirconium dimethyl;
9-silafluorendiylbis! 1 -[. 2-tert-butyl, 4-(2-methylphenyl)indenyl] } zirconium dimethyl;
9-silafluorendiylbis { 1 -[' 2-phenyl, 4-(2-methylphenyl)indenyl]} zirconium dimethyl;
9-silafluorendiylbis { l-[ 2-n-propyl, 4-(2-ethylphenyl)indenyl] } zirconium dimethyl;
9-silafluorendiylbis! 1 -[ 2-isopropyl, 4-(2-ethylphenyl)indenyl]} zirconium dimethyl;
9-silafluorendiylbis { l-[. 2-n-butyl, 4-(2-ethylphenyl)indenyl]} zirconium dimethyl;
9-silafluorendiylbis { 1 - [ 2-isobutyl, 4-(2-ethylphenyl)indenyl] } zirconium dimethyl;
9-silafluorendiylbis { 1 -[ 2-sec-butyl, 4-(2-ethylphenyl)indenyl]} zirconium dimethyl;
9-silafluorendiylbis { l-[ 2-tert-butyl, 4-(2-ethylphenyl)indenyl] } zirconium dimethyl;
9-silafluorendiylbis { 1 - [ 2-phenyl, 4-(2-ethylphenyl)indenyl]} zirconium dimethyl;
9-silafluorendiylbis { l-[ 2-n-propyl, 4-(2-n-propylphenyl)indeny 1] } zirconium dimethyl;
9-silafluorendiylbis { 1 -[ 2-isopropyl, 4-(2-n-propy lphenyl)indenyl] } zirconium dimethyl;
9-silafluorendiylbis { 1 -[ 2-n-butyl, 4-(2-n-propylphenyl)indenyl] } zirconium dimethyl;
9-silafluorendiylbis { l-[ 2-isobutyl, 4-(2-n-propylphenyl)indenyl]} zirconium dimethyl; 9-silafluorendiylbis 2-sec -butyl, 4-(2-n-propylphenyl)indenyl] } zirconium dimethyl;
9-silafluorendiylbis 2-tert-butyl, 4-(2-n-propylphenyl)indenyl] } zirconium dimethyl; 9-silafluorendiylbis 2-phenyl, 4-(2-n-propylphenyl)indenyl] } zirconium dimethyl;
9-silafluorendiylbis 2-n-propyl, 4-(2-isopropylphenyl)indenyl]} zirconium dimethyl;
9-silafluorendiylbis 2-isopropyl, 4-(2-isopropylphenyl)indenyl]} zirconium dimethyl;
9-silafluorendiylbis 2-n-butyl, 4-(2-isopropylphenyl)indenyl] } zirconium dimethyl;
9-silafluorendiylbis 2-isobutyl, 4-(2-isopropylphenyl)indenyl]} zirconium dimethyl; 9-silafluorendiylbis 1- 2-sec-butyl, 4-(2-isopropylphenyl)indenyl] } zirconium dimethyl;
9-silafluorendiylbis 1- 2-tert-butyl, 4-(2-isopropylphenyl)indenyl]} zirconium dimethyl;
9-silafluorendiylbis 1- 2-phenyl, 4-(2-isopropylphenyl)indenyl] } zirconium dimethyl;
9-silafluorendiylbis 1- 2-n-propyl, 4-(2-n-butylphenyl)indenyl]} zirconium dimethyl;
9-silafluorendiylbis 1- 2-isopropyl, 4-(2-n-butylphenyl)indenyl] } zirconium dimethyl; 9-silafluorendiylbis 1- 2-n-butyl, 4-(2-n-butylphenyl)indenyl] } zirconium dimethyl;
9-silafluorendiylbis 1- 2-isobutyl, 4-(2-n-butylphenyl)indenyl]} zirconium dimethyl;
9-silafluorendiylbis 1- 2-sec-butyl, 4-(2-n-butylphenyl)indenyl] } zirconium dimethyl;
9-silafluorendiylbis 1- 2-tert-butyl, 4-(2-n-butylphenyl)indenyl] } zirconium dimethyl; 9-silafluorendiylbis 2-phenyl, 4-(2-n-butylphenyl)indenyl] } zirconium dimethyl;
9-silafluorendiylbis 2-n-propyl, 4-(2-isobutylphenyl)indenyl] } zirconium dimethyl; 9-silafluorendiylbis 2-isopropyl, 4-(2-isobutylphenyl)indenyl] } zirconium dimethyl;
9-silafluorendiylbis 2-n-butyl, 4-(2-isobutylphenyl)indenyl] } zirconium dimethyl;
9-silafluorendiylbis 2-isobutyl, 4-(2-isobutylphenyl)indenyl] } zirconium dimethyl;
9-silafluorendiylbis 2-sec-butyl, 4-(2-isobutylphenyl)indenyl]} zirconium dimethyl;
9-silafluorendiylbis 2-tert-butyl, 4-(2-isobutylphenyl)indenyl] } zirconium dimethyl; 9-silafluorendiylbis 2-phenyl, 4-(2-isobutylphenyl)indenyl] } zirconium dimethyl;
9-silafluorendiylbis 2-n-propyl, 4-(2-sec-butylphenyl)indenyl] } zirconium dimethyl;
9-silafluorendiylbis 2-isopropyl, 4-(2-sec-buty lphenyl)indenyl] } zirconium dimethyl;
9-silafluorendiylbis 2-n-butyl, 4-(2-sec-butylphenyl)indenyl] } zirconium dimethyl;
9-silafluorendiylbis 2-isobutyl, 4-(2-sec-butylphenyl)indenyl]} zirconium dimethyl; 9-silafluorendiylbis 2-sec-butyl, 4-(2-sec-butylphenyl)indenyl] } zirconium dimethyl;
9-silafluorendiylbis 2-tert-butyl, 4-(2-sec-butylphenyl)indenyl] } zirconium dimethyl;
9-silafluorendiylbis 2-phenyl, 4-(2-sec-butylphenyl)indenyl]} zirconium dimethyl;
9-silafluorendiylbis 2-n-propyl, 4-(2-tert-butylphenyl)indenyl] } zirconium dimethyl; 9-silafluorendiylbis { 2-isopropyl, 4-(2-tert-butylphenyl)indenyl]} zirconium dimethyl;
9-silafluorendiylbis{ 2-n-butyl, 4-(2-tert-buty lpheny l)indeny 1] } zirconium dimethyl;
9-silafluorendiylbis { 2-isobutyl, 4-(2 -tert-buty lpheny l)indenyl] } zirconium dimethyl;
9-silafluorendiylbis { 2-sec-butyl, 4-(2-tert-butylphenyl)indenyl]} zirconium dimethyl;
9-silafluorendiylbis { 2-tert-butyl, 4-(2-tert-butylphenyl)indenyl] } zirconium dimethyl;
9-silafluorendiylbis { 2-phenyl, 4-(2-tert-buty lpheny l)indeny 1] } zirconium dimethyl;
9-silafluorendiylbis ! 2-n-propyl, 4-(2-biphenyl)indenyl]} zirconium dimethyl;
9-silafluorendiylbis{ 2-isopropyl, 4-(2-biphenyl)indenyl]} zirconium dimethyl;
9-silafluorendiylbis { 2-n-butyl, 4-(2-biphenyl)indenyl]} zirconium dimethyl;
9-silafluorendiylbis ! 2-isobutyl, 4-(2-biphenyl)indenyl]} zirconium dimethyl;
9-silafluorendiylbis { 2-sec-butyl, 4-(2-biphenyl)indenyl]} zirconium dimethyl;
9-silafluorendiylbis{ 2-tert-butyl, 4-(2-biphenyl)indenyl]} zirconium dimethyl;
9-silafluorendiylbis { 2-phenyl, 4-(2-biphenyl)indenyl]} zirconium dimethyl;
9-silafluorendiylbis { 2-n-propyl, 4-(2-α-naphthy lpheny l)indeny 1] } zirconium dimethyl;
9-silafluorendiylbis{ 2-isopropyl, 4-(2-α-naphthylphenyl)indenyl]} zirconium dimethyl;
9-silafluorendiylbis ! 2-n-butyl, 4-(2-α-naphthylphenyl)indenyl]} zirconium dimethyl;
9-silafluorendiylbis { 2-isobutyl, 4-(2-α-naphthy lpheny l)indeny 1] } zirconium dimethyl;
9-silafluorendiylbis { 2-sec-butyl, 4-(2-α-naphthylphenyl)indenyl] } zirconium dimethyl;
9-silafluorendiylbis { 2-tert-butyl, 4-(2-α-naphthy lpheny l)indenyl]} zirconium dimethyl; 9-silafluorendiylbis 2-pheny 1, 4-(2-α-naphthy lpheny l)indeny 1] } zirconium dimethyl;
9-silafluorendiylbis 1- 2-n-propyl, 4-(2-β-naphthylphenyl)indenyl] } zirconium dimethyl; 9-silafluorendiylbis 1- 2-isopropyl, 4-(2-β-naphthylphenyl)indenyl] } zirconium dimethyl;
9-silafluorendiylbis 1- 2-n-butyl, 4-(2-β-naphthy lpheny l)indenyl]} zirconium dimethyl;
9-silafluorendiylbis 1- 2-isobutyl, 4-(2-β-naphthylphenyl)indenyl] } zirconium dimethyl;
9-silafluorendiylbis 1- 2-sec-butyl, 4-(2-β-naphthylphenyl)indenyl]} zirconium dimethyl;
9-silafluorendiylbis 1- 2-tert-butyl, 4-(2-β-naphthylphenyl)indenyl]} zirconium dimethyl; 9-silafluorendiylbis 1- 2-phenyl, 4-(2-β-naphthylphenyl)indenyl]} zirconium dimethyl;
9-silafluorendiylbis 1- 2-n-propyl, 4-(2-trifluoromethylphenyl)indenyl] } zirconium dimethyl
9-silafluorendiylbis 1- 2-isopropyl, 4-(2 -trifluoromethy lpheny l)indenyl] } zirconium dimethyl
9-silafluorendiylbis 2-n-butyl, 4-(2-trifluoromethylphenyl)indenyl]} zirconium dimethyl;
9-silafluorendiylbis 1- 2-isobutyl, 4-(2-trifluoromethylphenyl)indenyl]} zirconium dimethyl; 9-silafluorendiylbis 1- 2-sec-butyl, 4-(2 -trifluoromethy lphenyl)indenyl] } zirconium dimethyl
9-silafluorendiylbis 2-tert-butyl, 4-(2-trifluoromethylphenyl)indenyl] } zirconium dimethyl
9-silafluorendiylbis 2-phenyl, 4-(2 -trifluoromethy lpheny l)indenyl]} zirconium dimethyl;
9-silafluorendiylbis 2-n-propyl, 4-(2-trimethylsilylphenyl)indenyl] } zirconium dimethyl; 9-silafluorendiylbis 2-isopropyl, 4-(2-trimethylsilylphenyl)indenyl] } zirconium dimethyl;
9-silafluorendiylbis 2-n-butyl, 4-(2-trimethylsilylphenyl)indenyl] } zirconium dimethyl;
9-silafluorendiylbis 2-isobutyl, 4-(2-trimethylsilylphenyl)indenyl] } zirconium dimethyl;
9-silafluorendiylbis 2-sec-butyl, 4-(2-trimethylsilylphenyl)indenyl] } zirconium dimethyl;
9-silafluorendiylbis 2-tert-butyl, 4-(2-trimethylsilylphenyl)indenyl] }zirconium dimethyl;
9-silafluorendiylbis 2-phenyl, 4-(2 -trimethylsily lpheny l)indenyl] } zirconium dimethyl;
9-silafluorendiylbis 1- 2-n-propyl, 4-(2,3 -dimethylphenyl)indenyl] } zirconium dimethyl;
9-silafluorendiylbis 2-isopropyl, 4-(2, 3 -dimethy lphenyl)indenyl] } zirconium dimethyl;
9-silafluorendiylbis 2-n-butyl, 4-(2,3-dimethylphenyl)indenyl] } zirconium dimethyl;
9-silafluorendiylbis 2-isobutyl, 4-(2,3-dimethylphenyl)indenyl]}zirconium dimethyl;
9-silafluorendiylbis 2-sec-butyl, 4-(2,3-dimethylphenyl)indenyl]} zirconium dimethyl;
9-silafluorendiylbis 2-tert-butyl, 4-(2,3-dimethylphenyl)indenyl] }zirconium dimethyl;
9-silafluorendiylbis 1- 2-phenyl, 4-(2,3 -dimethy lphenyl)indenyl] } zirconium dimethyl;
9-silafluorendiylbis 1- 2-n-propyl, 4-(2, 3, 4-trimethylphenyl)indenyl]} zirconium dimethyl;
9-silafluorendiylbis 1- 2-isopropyl, 4-(2,3,4-trimethylphenyl)indenyl]}zirconium dimethyl;
9-silafluorendiylbis 1- 2-n-butyl, 4-(2,3,4-trimethylphenyl)indenyl] }zirconium dimethyl; 9-silafluorendiylbis 2-isobutyl, 4-(2,3,4-trimethylphenyl)indenyl]}zirconium dimethyl;
9-silafluorendiylbis 2-sec-butyl, 4-(2,3,4-trimethylphenyl)indenyl]} zirconium dimethyl
9-silafluorendiylbis 2-tert-butyl, 4-(2,3,4-trimethylphenyl)indenyl] } zirconium dimethyl
9-silafluorendiylbis 1- 2-phenyl, 4-(2,3,4-trimethylphenyl)indenyl]}zirconium dimethyl;
9-silafluorendiylbis 1- 2-n-propyl, 4-(2,3,5-trimethylphenyl)indenyl]}zirconium dimethyl;
9-silafluorendiylbis 1- 2-isopropyl, 4-(2,3,5-trimethylphenyl)indenyl]}zirconium dimethyl;
9-silafluorendiylbis 1- 2-n-butyl, 4-(2,3,5-trimethylphenyl)indenyl] } zirconium dimethyl;
9-silafluorendiylbis 2-isobutyl, 4-(2,3,5-trimethylphenyl)indenyl]}zirconium dimethyl;
9-silafluorendiylbis 1- 2-sec-butyl, 4-(2,3 ,5-trimethylphenyl)indenyl] } zirconium dimethyl;
9-silafluorendiylbis 2-tert-butyl, 4-(2,3,5-trimethylphenyl)indenyl]}zirconium dimethyl;
9-silafluorendiylbis 2-phenyl, 4-(2,3,5-trimethylphenyl)indenyl]}zirconium dimethyl;
9-silafluorendiylbis 2-n-propyl, 4-(2-methylphenyl)indenyl] } hafnium dichloride;
9-silafluorendiylbis 2-isopropyl, 4-(2-methy lpheny l)indenyl]} hafnium dichloride;
9-silafluorendiylbis 2-n-butyl, 4-(2-methylphenyl)indenyl] } hafnium dichloride;
9-silafluorendiylbis 2-isobutyl, 4-(2-methylphenyl)indenyl]} hafnium dichloride;
9-silafluorendiylbis 2-sec-butyl, 4-(2-methylphenyl)indenyl] } hafnium dichloride; 9-silafluorendiylbis! 1 -[2-tert-butyl, 4-(2-methylphenyl)indenyl]} hafnium dichloride;
9-silafluorendiylbis 2-phenyl, 4-(2-methylphenyl)indenyl]} hafnium dichloride;
9-silafluorendiylbis 2-n-propyl, 4-(2-ethylphenyl)indenyl]} hafnium dichloride;
9-silafluorendiylbis 2-isopropyl, 4-(2-ethylphenyl)indenyl] } hafnium dichloride;
9-silafluorendiylbis 2-n-butyl, 4-(2-ethylphenyl)indenyl]}hafnium dichloride;
9-silafluorendiylbis 2-isobutyl, 4-(2-ethylphenyl)indenyl]} hafnium dichloride;
9-silafluorendiylbis 2-sec-butyl, 4-(2-ethylphenyl)indenyl] } hafnium dichloride;
9-silafluorendiylbis 2-tert-butyl, 4-(2-ethylphenyl)indenyl]} hafnium dichloride;
9-silafluorendiylbis 2-phenyl, 4-(2-ethylphenyl)indenyl]} hafnium dichloride;
9-silafluorendiylbis 2-n-propyl, 4-(2-n-propy lpheny l)indenyl] } hafnium dichloride;
9-silafluorendiylbis 2-isopropyl, 4-(2-n-propylpheny l)indeny 1] } hafnium dichloride;
9-silafluorendiylbis 2-n-butyl, 4-(2-n-propylphenyl)indenyl] } hafnium dichloride;
9-silafluorendiylbis 2-isobutyl, 4-(2-n-propy lpheny l)indenyl] } hafnium dichloride;
9-silafluorendiylbis 2-sec-butyl, 4-(2-n-propylphenyl)indenyl] } hafnium dichloride;
9-silafluorendiylbis 2-tert-butyl, 4-(2-n-propylphenyl)indenyl] } hafnium dichloride;
9-silafluorendiylbis 2-phenyl, 4-(2-n-propylphenyl)indenyl] } hafnium dichloride;
9-silafluorendiylbis 2-n-propyl, 4-(2-isopropylphenyl)indenyl] }hafhium dichloride;
9-silafluorendiylbis 2-isopropyl, 4-(2-isopropylphenyl)indenyl]} hafnium dichloride; 9-silafluorendiylbis 1- 2-n-butyl, 4-(2-isopropylphenyl)indenyl]} hafnium dichloride;
9-silafluorendiylbis 1- 2-isobutyl, 4-(2-isopropylphenyl)indenyl] }hafnium dichloride;
9-silafluorendiylbis 1- 2-sec-butyl, 4-(2-isopropylphenyl)indenyl] } hafnium dichloride;
9-silafluorendiylbis 1- 2-tert-butyl, 4-(2-isopropylphenyl)indenyl] } hafnium dichloride;
9-silafluorendiylbis 1- 2-phenyl, 4-(2-isopropylphenyl)indenyl]} hafnium dichloride;
9-silafluorendiylbis 1- 2-n-propyl, 4-(2-n-butylphenyl)indenyl] } hafnium dichloride;
9-silafluorendiylbis 1- 2-isopropyl, 4-(2-n-butylphenyl)indenyl] } hafnium dichloride;
9-silafluorendiylbis 1- 2-n-butyl, 4-(2-n-butylphenyl)indenyl] } hafnium dichloride;
9-silafluorendiylbis 1- 2-isobutyl, 4-(2-n-butylpheny l)indenyl] } hafnium dichloride;
9-silafluorendiylbis 1- 2-sec-butyl, 4-(2-n-butylphenyl)indenyl] }hafnium dichloride;
9-silafluorendiylbis 1- 2-tert-butyl, 4-(2-n-butylphenyl)indenyl] } hafnium dichloride;
9-silafluorendiylbis 1- 2-phenyl, 4-(2-n-butylphenyl)indenyl] } hafnium dichloride;
9-silafluorendiylbis 2-n-propyl, 4-(2-isobutylphenyl)indenyl]}hafnium dichloride;
9-silafluorendiylbis 2-isopropyl, 4-(2-isobutylphenyl)indenyl]} hafnium dichloride;
9-silafluorendiylbis 2-n-butyl, 4-(2-isobutylphenyl)indenyl]} hafnium dichloride;
9-silafluorendiylbis 2-isobutyl, 4-(2-isobutylphenyl)indenyl]}hafnium dichloride; 9-silafluorendiylbis 2-sec-butyl, 4-(2-isobutylphenyl)indenyl] }hafnium dichloride;
9-silafluorendiylbis 2-tert-butyl, 4-(2-isobutylphenyl)indenyl]} hafnium dichloride;
9-silafluorendiylbis 2-phenyl, 4-(2-isobuty lpheny l)indeny 1] } hafnium dichloride;
9-silafluorendiylbis 2-n-propyl, 4-(2-sec-butylphenyl)indenyl] } hafnium dichloride;
9-silafluorendiylbis 2-isopropyl, 4-(2-sec-butylphenyl)indenyl]} hafnium dichloride;
9-silafluorendiylbis 2-n-butyl, 4-(2-sec-butylphenyl)indenyl] } hafnium dichloride;
9-silafluorendiylbis 2-isobutyl, 4-(2-sec-butylphenyl)indenyl] } hafnium dichloride;
9-silafluorendiylbis 2-sec-butyl, 4-(2-sec-butylphenyl)indenyl]} hafnium dichloride;
9-silafluorendiylbis 2-tert-butyl, 4-(2-sec-butylphenyl)indenyl]} hafnium dichloride;
9-silafluorendiylbis 2-phenyl, 4-(2-sec-butylphenyl)indenyl] } hafnium dichloride;
9-silafluorendiylbis 2-n-propyl, 4-(2-tert-butylphenyl)indenyl] }hafnium dichloride;
9-silafluorendiylbis 2-isopropyl, 4-(2-tert-butylphenyl)indenyl] } hafnium dichloride;
9-silafluorendiylbis 2-n-butyl, 4-(2-tert-butylphenyl)indenyl] } hafnium dichloride;
9-silafluorendiylbis 2-isobutyl, 4-(2-tert-butylphenyl)indenyl] } hafnium dichloride;
9-silafluorendiylbis 2-sec-butyl, 4-(2 -tert-buty lphenyl)indenyl] } hafnium dichloride;
9-silafluorendiylbis 2-tert-butyl, 4-(2-tert-butylphenyl)indenyl]} hafnium dichloride; 9-silafluorendiylbis { 1 -[2-phenyl, 4-(2-tert-butylphenyl)indenyl]} hafnium dichloride;
9-silafluorendiylbis{ 1- 2-n-propyl, 4-(2-biphenyl)indenyl]}hafnium dichloride;
9-silafluorendiylbis{ 1- 2-isopropyl, 4-(2-biphenyl)indenyl]} hafnium dichloride; 9-silafluorendiylbis ! 1 - 2-n-butyl, 4-(2-biphenyl)indenyl]} hafnium dichloride;
9-silafluorendiylbis { 1- 2-isobutyl, 4-(2-biphenyl)indenyl]} hafnium dichloride;
9-silafluorendiylbis{ 1 - 2-sec-butyl, 4-(2-biphenyl)indenyl]} hafnium dichloride;
9-silafluorendiylbis! 1- 2-tert-butyl, 4-(2-biphenyl)indenyl]} hafnium dichloride;
9-silafluorendiylbis ! 1 - 2-phenyl, 4-(2-biphenyl)indenyl]} hafnium dichloride; 9-silafluorendiylbis { 1 - 2-n-propyl, 4-(2-α-naphthylphenyl)indenyl] }hafnium dichloride;
9-silafluorendiylbis { 1 - 2-isopropyl, 4-(2-α-naphthy lpheny l)indenyl] } hafnium dichloride;
9-silafluorendiylbis { 1 - 2-n-butyl, 4-(2-α-naphthy lpheny l)indenyl]} hafnium dichloride;
9-silafluorendiylbis { 1 - 2-isobutyl, 4-(2-α-naphthylphenyl)indenyl] }hafnium dichloride;
9-silafluorendiylbis { 1 - 2-sec-butyl, 4-(2-α-naphthylphenyl)indenyl]} hafnium dichloride; 9-silafluorendiylbis { 1 - 2-tert-butyl, 4-(2-α-naphthy lpheny l)indeny 1] } hafnium dichloride;
9-silafluorendiylbis { 1 - 2-phenyl, 4-(2-α-naphthy lpheny l)indeny 1] } hafnium dichloride;
9-silafluorendiylbis! 1 - 2-n-propyl, 4-(2-β-naphthylphenyl)indenyl] }hafnium dichloride;
9-silafluorendiylbis { 1 - 2-isopropyl, 4-(2-β-naphthy lpheny l)indenyl] } hafnium dichloride;
9-silafluorendiylbis! 1 - 2-n-butyl, 4-(2-β-naphthylphenyl)indenyl]}hafnium dichloride; 9-silafluorendiylbis! 1- 2-isobutyl, 4-(2-β-naphthylphenyl)indenyl]}hafnium dichloride; 9-silafluorendiylbis 2-sec-butyl, 4-(2-β-naphthylphenyl)indenyl] }hafnium dichloride;
9-silafluorendiylbis 1- 2-tert-butyl, 4-(2-β-naphthy lpheny l)indenyl] } hafnium dichloride;
9-silafluorendiylbis 1- 2-phenyl, 4-(2-β-naphthy lpheny l)indenyl]} hafnium dichloride;
9-silafluorendiylbis 1- 2-n-propyl, 4-(2-trifluoromethy lpheny l)indeny 1] } hafnium dichloride;
9-silafluorendiylbis 1- 2-isopropyl, 4-(2-trifluoromethylphenyl)indenyl]}hafnium dichloride;
9-silafluorendiylbis 1- 2-n-butyl, 4-(2-trifluoromethylphenyl)indenyl] } hafnium dichloride;
9-silafluorendiylbis 1- 2-isobutyl, 4-(2 -trifluoromethy lphenyl)indeny 1] } hafnium dichloride;
9-silafluorendiylbis 1- 2-sec-butyl, 4-(2-trifluoromethylphenyl)indenyl]}hafnium dichloride;
9-silafluorendiylbis 1- 2-tert-butyl, 4-(2-trifluoromethylphenyl)indenyl] } hafnium dichloride;
9-silafluorendiylbis 1- 2-phenyl, 4-(2-trifluoromethylphenyl)indenyl] }hafnium dichloride;
9-silafluorendiylbis 1- 2-n-propyl, 4-(2-trimethylsilylphenyl)indenyl] }hafnium dichloride;
9-silafluorendiylbis 1- 2-isopropyl, 4-(2-trimethylsily lphenyl)indeny 1] } hafnium dichloride;
9-silafluorendiylbis 1- 2-n-butyl, 4-(2-trimethylsilylphenyl)indenyl]} hafnium dichloride;
9-silafluorendiylbis 1- 2-isobutyl, 4-(2 -trimethy lsilylphenyl)indenyl]} hafnium dichloride;
9-silafluorendiylbis 1- 2-sec-butyl, 4-(2-trimethylsilylphenyl)indenyl]}hafnium dichloride;
9-silafluorendiylbis 1- 2-tert-butyl, 4-(2-trimethylsilylphenyl)indenyl] } hafnium dichloride; 9-silafluorendiylbis 2-phenyl, 4-(2 -trimethy lsily lpheny l)indenyl] } hafnium dichloride;
9-silafluorendiylbis 2-n-propyl, 4-(2,3-dimethylphenyl)indenyl]}hafnium dichloride;
9-silafluorendiylbis 2-isopropyl, 4-(2,3-dimethylphenyl)indenyl]}hafnium dichloride;
9-silafluorendiylbis 2-n-butyl, 4-(2,3-dimethylphenyl)indenyl] }hafnium dichloride;
9-silafluorendiylbis 2-isobutyl, 4-(2,3-dimethylphenyl)indenyl]}hafnium dichloride;
9-silafluorendiylbis 2-sec-butyl, 4-(2,3-dimethylphenyl)indenyl]}hafnium dichloride;
9-silafluorendiylbis 2-tert-butyl, 4-(2,3-dimethylphenyl)indenyl]} hafnium dichloride;
9-silafluorendiylbis 2-phenyl, 4-(2,3-dimethylphenyl)indenyl]}hafnium dichloride;
9-silafluorendiylbis 2-n-propyl, 4-(2,3,4-trimethylphenyl)indenyl]}hafnium dichloride;
9-silafluorendiylbis 2-isopropyl, 4-(2,3,4-trimethylphenyl)indenyl]} hafnium dichloride;
9-silafluorendiylbis 2-n-butyl, 4-(2,3,4-trimethylphenyl)indenyl] }hafnium dichloride;
9-silafluorendiylbis 2-isobutyl, 4-(2,3, 4-trimethy lphenyl)indenyl]} hafnium dichloride;
9-silafluorendiylbis 2-sec-butyl, 4-(2,3,4-trimethylphenyl)indenyl]}hafnium dichloride;
9-silafluorendiylbis 2-tert-butyl, 4-(2,3,4-trimethylphenyl)indenyl] }hafnium dichloride;
9-silafluorendiylbis 2-phenyl, 4-(2,3,4-trimethylphenyl)indenyl] }hafnium dichloride;
9-silafluorendiylbis 2-n-propyl, 4-(2,3,5-trimethylphenyl)indenyl]}hafnium dichloride; 9-silafluorendiylbis { 2-isopropyl, 4-(2, 3, 5-trimethylphenyl)indenyl]}hafnium dichloride;
9-silafluorendiylbis { 2-n-butyl, 4-(2, 3, 5-trimethylphenyl)indenyl]} hafnium dichloride; 9-silafluorendiylbis { 2-isobutyl, 4-(2,3,5-trimethylphenyl)indenyl] }hafnium dichloride;
9-silafluorendiylbis { 2-sec-butyl, 4-(2,3,5-trimethylphenyl)indenyl]}hafnium dichloride;
9-silafluorendiylbis { 2-tert-butyl, 4-(2,3,5-trimethylphenyl)indenyl] }hafnium dichloride;
9-silafluorendiylbis { 2-phenyl, 4-(2,3,5-trimethylphenyl)indenyl] }hafnium dichloride;
9-silafluorendiylbis ! 2-n-propyl, 4-(2-methylphenyl)indenyl] }hafnium dimethyl; 9-silafluorendiylbis! 2-isopropyl, 4-(2-methylphenyl)indenyl] }hafnium dimethyl;
9-silafluorendiylbis { 2-n-butyl, 4-(2-methylphenyl)indenyl]} hafnium dimethyl;
9-silafluorendiylbis { 2-isobutyl, 4-(2-methylphenyl)indenyl] } hafnium dimethyl;
9-silafluorendiylbis ! 2-sec-butyl, 4-(2-methylphenyl)indenyl] }hafnium dimethyl;
9-silafluorendiylbis { 2-tert-butyl, 4-(2-methylphenyl)indenyl]} hafnium dimethyl;
9-silafluorendiylbis { 2-phenyl, 4-(2-methylphenyl)indenyl]} hafnium dimethyl;
9-silafluorendiylbis ! 2-n-propyl, 4-(2-ethylphenyl)indenyl]} hafnium dimethyl; 9-silafluorendiylbis { 2-isopropyl, 4-(2-ethylphenyl)indenyl]}hafnium dimethyl;
9-silafluorendiylbis ! 2-n-butyl, 4-(2-ethy lpheny l)indenyl]} hafnium dimethyl;
9-silafluorendiylbis ! 2-isobutyl, 4-(2-ethy lpheny l)indenyl]} hafnium dimethyl;
9-silafluorendiy Ibis { 2-sec-butyl, 4-(2-ethylphenyl)indenyl]} hafnium dimethyl;
9-silafluorendiylbis { 2-tert-butyl, 4-(2-ethylphenyl)indenyl]} hafnium dimethyl; 9-silafluorendiylbis { 2-phenyl, 4-(2-ethylphenyl)indenyl]} hafnium dimethyl;
9-silafluorendiylbis { 2-n-propyl, 4-(2-n-propylρhenyl)indenyl] } hafnium dimethyl; 9-silafluorendiylbis { 1 -[ 2-isopropyl, 4-(2-n-propylphenyl)indenyl] } hafnium dimethyl;
9-silafluorendiylbis { l-[. 2-n-butyl, 4-(2-n-propylphenyl)indenyl] } hafnium dimethyl;
9-silafluorendiylbis { \-[. 2-isobutyl, 4-(2-n-propylphenyl)indenyl] } hafnium dimethyl;
9-silafluorendiylbis! 1 -[ 2-sec-butyl, 4-(2-n-propylphenyl)indenyl] }hafnium dimethyl;
9-silafluorendiylbis { 1 -[ 2-tert-butyl, 4-(2-n-propylphenyl)indenyl] } hafnium dimethyl;
9-silafluorendiylbis { l-[ 2-phenyl, 4-(2-n-propylphenyl)indeny 1] } hafnium dimethyl;
9-silafluorendiylbis { l-[ 2-n-propyl, 4-(2-isopropylphenyl)indenyl] } hafnium dimethyl;
9-silafluorendiylbis { 1 - [ 2-isopropyl, 4-(2-isopropylphenyl)indenyl]} hafnium dimethyl;
9-silafluorendiylbis{ 1 -[ 2-n-butyl, 4-(2-isopropylphenyl)indenyl] } hafnium dimethyl;
9-silafluorendiylbis { l-[ 2-isobutyl, 4-(2-isopropylphenyl)indenyl] } hafnium dimethyl;
9-silafluorendiylbis! 1 -[ 2-sec-butyl, 4-(2-isopropylphenyl)indenyl]} hafnium dimethyl;
9-silafluorendiylbis { 1 -[ 2-tert-butyl, 4-(2-isopropy lphenyl)indenyl] } hafnium dimethyl;
9-silafluorendiylbis { 1 -[ 2-phenyl, 4-(2-isopropylphenyl)indenyl]} hafnium dimethyl;
9-silafluorendiylbis { l-[ 2-n-propyl, 4-(2-n-buty lpheny l)indeny 1] } hafnium dimethyl;
9-silafluorendiylbis { 1 -[ 2-isopropyl, 4-(2-n-butylphenyl)indenyl]} hafnium dimethyl;
9-silafluorendiylbis { l-[ 2-n-butyl, 4-(2-n-butylphenyl)indenyl]} hafnium dimethyl; 9-silafluorendiylbis { 1 -[ 2-isobutyl, 4-(2-n-butylphenyl)indenyl] } hafnium dimethyl;
9-silafluorendiylbis{ l-[ 2-sec-butyl, 4-(2-n-butylphenyl)indenyl] }hafnium dimethyl;
9-silafluorendiylbis { 1 -[ 2-tert-butyl, 4-(2-n-buty lpheny l)indenyl] } hafnium dimethyl;
9-silafluorendiylbis { 1 - [ 2-phenyl, 4-(2-n-butylphenyl)indenyl]} hafnium dimethyl;
9-silafluorendiylbis { l-[ 2-n-propyl, 4-(2-isobuty lpheny l)indenyl] } hafnium dimethyl;
9-silafluorendiylbis! 1 -[ 2-isopropyl, 4-(2-isobutylphenyl)indenyl]} hafnium dimethyl;
9-silafluorendiylbis { 1 -[ 2-n-butyl, 4-(2-isobutylphenyl)indenyl] } hafnium dimethyl;
9-silafluorendiylbis {l-[ 2-isobutyl, 4-(2-isobuty lpheny l)indenyl] } hafnium dimethyl;
9-silafluorendiylbis { 1 -[ 2-sec-butyl, 4-(2-isobutylphenyl)indenyl]} hafnium dimethyl;
9-silafluorendiylbis { 1 -[ 2-tert-butyl, 4-(2-isobutylphenyl)indenyl] } hafnium dimethyl;
9-silafluorendiylbis { 1 -[ 2-phenyl, 4-(2-isobutylphenyl)indenyl]} hafnium dimethyl;
9-silafluorendiylbis { 1 -[ 2-n-propyl, 4-(2-sec-butylphenyl)indenyl] } hafnium dimethyl;
9-silafluorendiylbis! l-[ 2-isopropyl, 4-(2-sec-buty lpheny l)indeny 1] } hafnium dimethyl;
9-silafluorendiylbis { l-[ 2-n-butyl, 4-(2-sec-butylphenyl)indenyl]} hafnium dimethyl;
9-silafluorendiylbis { l-[ 2-isobutyl, 4-(2-sec-buty lpheny l)indenyl]} hafnium dimethyl;
9-silafluorendiylbis! l-[ 2-sec-butyl, 4-(2-sec-butylphenyl)indenyl]} hafnium dimethyl;
9-silafluorendiylbis { 1 -[ 2-tert-butyl, 4-(2-sec-butylphenyl)indenyl] } hafnium dimethyl; 9-silafluorendiylbis ! 2-phenyl, 4-(2-sec-butylphenyl)indenyl] } hafnium dimethyl;
9-silafluorendiylbis { 2-n-propyl, 4-(2-tert-butylphenyl)indenyl] }hafnium dimethyl; 9-silafluorendiylbis! 2-isopropyl, 4-(2-tert-butylphenyl)indenyl] } hafnium dimethyl;
9-silafluorendiylbis { 2-n-butyl, 4-(2-tert-buty lphenyl)indeny 1] } hafnium dimethyl;
9-silafluorendiylbis { 2-isobutyl, 4-(2-tert-butylpheny l)indenyl] } hafnium dimethyl;
9-silafluorendiylbis { 2-sec-butyl, 4-(2-tert-butylphenyl)indenyl] } hafnium dimethyl;
9-silafluorendiylbis { 2-tert-butyl, 4-(2 -tert-buty lpheny l)indenyl] } hafnium dimethyl; 9-silafluorendiylbis { 2-phenyl, 4-(2 -tert-buty lphenyl)indenyl] } hafnium dimethyl;
9-silafluorendiylbis { 2-n-propyl, 4-(2-biphenyl)indenyl]} hafnium dimethyl;
9-silafluorendiylbis! 2-isopropyl, 4-(2-biphenyl)indenyl]} hafnium dimethyl;
9-silafluorendiylbis { 2-n-butyl, 4-(2-biphenyl)indenyl]} hafnium dimethyl; 9-silafluorendiylbis { 2-isobutyl, 4-(2-biphenyl)indenyl]} hafnium dimethyl;
9-silafluorendiylbis! 2-sec-butyl, 4-(2-biphenyl)indenyl]}hafnium dimethyl;
9-silafluorendiylbis { 2-tert-butyl, 4-(2-biphenyl)indenyl]}hafnium dimethyl;
9-silafluorendiylbis { 2-phenyl, 4-(2-biphenyl)indenyl]} hafnium dimethyl;
9-silafluorendiylbis! 2-n-propyl, 4-(2-α-naphthylphenyl)indenyl] }hafnium dimethyl;
9-si lafluorendiy lbi s { 2-isopropyl, 4-(2-α-naphthylphenyl)indenyl]} hafnium dimethyl;
9-silafluorendiylbis ! 2-n-butyl, 4-(2-α-naphthy lpheny l)indenyl]} hafnium dimethyl; 9-silafluorendiylbis { 2-isobutyl, 4-(2-α-naphthy lpheny l)indenyl]} hafnium dimethyl; 9-silafluorendiylbis 2-sec-butyl, 4-(2-α-naphthy lpheny l)indenyl] } hafnium dimethyl;
9-si lafluorendiy Ibis 1- 2-tert-butyl, 4-(2-α-naphthy lpheny l)indeny 1] } hafnium dimethyl;
9-silafluorendiylbis 1- 2-phenyl, 4-(2-α-naphthylphenyl)indenyl] } hafnium dimethyl;
9-silafluorendiylbis 1- 2-n-propyl, 4-(2-β-naphthy lpheny l)indenyl] } hafnium dimethyl;
9-silafluorendiylbis 2-isopropyl, 4-(2-β-naphthy lpheny l)indeny 1] } hafnium dimethyl;
9-silafluorendiylbis 2-n-butyl, 4-(2-β-naphthylphenyl)indenyl] } hafnium dimethyl;
9-silafluorendiylbis 1- 2-isobutyl, 4-(2-β-naphthy lpheny l)indenyl] } hafnium dimethyl;
9-silafluorendiylbis 2-sec-butyl, 4-(2-β-naphthy lpheny l)indeny 1] } hafnium dimethyl;
9-silafluorendiylbis 2-tert-butyl, 4-(2-β-naphthy lpheny l)indenyl]} hafnium dimethyl;
9-silafluorendiylbis 2-phenyl, 4-(2-β-naphthylphenyl)indeny 1] } hafnium dimethyl;
9-silafluorendiylbis 2-n-propyl, 4-(2-trifluoromethylphenyl)indenyl]}hafnium dimethyl;
9-silafluorendiylbis 2-isopropyl, 4-(2-trifluoromethylphenyl)indenyl]} hafnium dimethyl;
9-silafluorendiylbis 1- 2-n-butyl, 4-(2 -trifluoromethy lpheny l)indeny 1] } hafnium dimethyl;
9-silafluorendiylbis 1- 2-isobutyl, 4-(2-trifluoromethylphenyl)indenyl]} hafnium dimethyl;
9-silafluorendiylbis 1- 2-sec-butyl, 4-(2-trifluoromethylphenyl)indenyl]} hafnium dimethyl;
9-silafluorendiylbis 1- 2-tert-butyl, 4-(2-trifluoromethy lpheny l)indenyl] } hafnium dimethyl; - 12 -
9-silafluorendiylbis 1- 2-phenyl, 4-(2-trifluoromethylphenyl)indenyl] } hafnium dimethyl;
9-silafluorendiylbis 2-n-propyl, 4-(2-trimethylsilylphenyl)indenyl] } hafnium dimethyl;
9-silafluorendiylbis 2-isopropyl, 4-(2-trimethylsily lpheny l)indeny 1] } hafnium dimethyl;
9-silafluorendiylbis 1- 2-n-butyl, 4-(2-trimethylsily lpheny l)indenyl] } hafnium dimethyl;
9-silafluorendiylbis 1- 2-isobutyl, 4-(2-trimethylsilylphenyl)indenyl]}hafnium dimethyl;
9-silafluorendiy lbi s 1- 2-sec-butyl, 4-(2-trimethylsilylphenyl)indenyl] } hafnium dimethyl;
9-silafluorendiylbis 1- 2-tert-butyl, 4-(2-trimethylsily lpheny l)indenyl] } hafnium dimethyl;
9-silafluorendiylbis 1- 2-phenyl, 4-(2 -trimethy lsilylpheny l)indenyl] } hafnium dimethyl;
9-silafluorendiylbis 1- 2-n-propyl, 4-(2,3-dimethylphenyl)indenyl] }hafnium dimethyl;
9-silafluorendiylbis 1- 2-isopropyl, 4-(2,3-dimethylphenyl)indenyl]} hafnium dimethyl;
9-silafluorendiylbis 1- 2-n-butyl, 4-(2,3-dimethylphenyl)indenyl]}hafnium dimethyl;
9-silafluorendiylbis 1- 2-isobutyl, 4-(2,3-dimethylphenyl)indenyl] }hafnium dimethyl;
9-silafluorendiylbis 1- 2-sec-butyl, 4-(2,3-dimethylphenyl)indenyl]}hafnium dimethyl;
9-silafluorendiylbis 1- 2-tert-butyl, 4-(2,3-dimethylphenyl)indenyl]}hafnium dimethyl;
9-silafluorendiylbis 1- 2-phenyl, 4-(2,3-dimethylphenyl)indenyl]}hafnium dimethyl;
9-silafluorendiylbis 2-n-propyl, 4-(2,3,4-trimethylphenyl)indenyl]}hafnium dimethyl; 9-silafluorendiylbis 2-isopropyl, 4-(2,3,4-trimethylphenyl)indenyl]} hafnium dimethyl;
9-silafluorendiylbis 2-n-butyl, 4-(2,3,4-trimethylphenyl)indenyl]} hafnium dimethyl;
9-silafluorendiylbis 2-isobutyl, 4-(2,3,4-trimethylphenyl)indenyl] }hafnium dimethyl;
9-silafluorendiylbis 1- 2-sec-butyl, 4-(2,3,4-trimethylphenyl)indenyl]}hafnium dimethyl;
9-silafluorendiylbis 1- 2-tert-butyl, 4-(2,3,4-trimethylphenyl)indenyl] }hafnium dimethyl;
9-silafluorendiylbis 1- 2-phenyl, 4-(2,3,4-trimethylphenyl)indenyl]}hafnium dimethyl;
9-silafluorendiylbis 1- 2-n-propyl, 4-(2,3,5-trimethylphenyl)indenyl]}hafnium dimethyl;
9-silafluorendiylbis 1- 2-isopropyl, 4-(2,3,5-trimethylphenyl)indenyl]}hafnium dimethyl;
9-silafluorendiylbis 1- 2-n-butyl, 4-(2,3,5-trimethylphenyl)indenyl]}hafnium dimethyl;
9-silafluorendiylbis 2-isobutyl, 4-(2,3 ,5 -trimethy lphenyl)indenyl] } hafnium dimethyl;
9-silafluorendiylbis 2-sec-butyl, 4-(2,3,5-trimethylphenyl)indenyl]}hafnium dimethyl;
9-silafluorendiylbis 2-tert-butyl, 4-(2,3,5-trimethylphenyl)indenyl] }hafnium dimethyl;
9-silafluorendiylbis 2-phenyl, 4-(2,3,5-trimethylphenyl)indenyl] }hafnium dimethyl; dimethylamidoboranebis! 1 -[2-n-propyl, 4-(2-methylphenyl)indenyl]} zirconium dichloride; dimethylamidoboranebis! 1 -[2-isopropyl, 4-(2-methylphenyl)indenyl] } zirconium dichloride; dimethylamidoboranebis ! 1 - [2-n-butyl, 4-(2-methylphenyl)indenyl] } zirconium dichloride; dimethylamidoboranebis 1- 2-isobutyl, 4-(2-methy lphenyl)indenyl] } zirconium dichloride; dimethylamidoboranebis 1- 2-sec-butyl, 4-(2-methylphenyl)indenyl]} zirconium dichloride; dimethy lamidoboranebi s 1- 2-tert-butyl, 4-(2-methy lpheny l)indeny 1] } zirconium dichloride; dimethylamidoboranebis 2-phenyl, 4-(2-methylphenyl)indenyl] } zirconium dichloride; dimethylamidoboranebis 1- 2-n-propyl, 4-(2-ethylphenyl)indenyl] } zirconium dichloride; dimethy lamidoboranebi s 1- 2-isopropyl, 4-(2-ethylphenyl)indenyl] } zirconium dichloride; dimethylamidoboranebis 1- 2-n-butyl, 4-(2-ethy lphenyl)indenyl] } zirconium dichloride; dimethylamidoboranebis 1- 2-isobutyl, 4-(2-ethylphenyl)indenyl] } zirconium dichloride; dimethylamidoboranebis 2-sec-butyl, 4-(2-ethylphenyl)indenyl]} zirconium dichloride; dimethylamidoboranebis 2-tert-butyl, 4-(2-ethylphenyl)indenyl] } zirconium dichloride; dimethylamidoboranebis 2-phenyl, 4-(2-ethy lphenyl)indenyl] } zirconium dichloride; dimethylamidoboranebis 2-n-propyl, 4-(2-n-propylphenyl)indenyl] } zirconium dichloride; dimethylamidoboranebis 2-isopropyl, 4-(2-n-propylphenyl)indenyl] } zirconium dichloride; dimethylamidoboranebis 1- 2-n-butyl, 4-(2 -n-propy lphenyl)indenyl] } zirconium dichloride; dimethylamidoboranebis 1- 2-isobutyl, 4-(2-n-propylphenyl)indeny 1] } zirconium dichloride; dimethylamidoboranebis 2-sec-butyl, 4-(2-n-propylphenyl)indenyl]}zirconium dichloride; dimethylamidoboranebis 1- 2-tert-butyl, 4-(2-n-propylphenyl)indenyl] } zirconium dichloride; dimethylamidoboranebis 2-phenyl, 4-(2-n-propylphenyl)indenyl] } zirconium dichloride; dimethylamidoboranebis 2-n-propyl, 4-(2-isopropylphenyl)indenyl]} zirconium dichloride; dimethylamidoboranebis 2-isopropyl, 4-(2-isopropylphenyl)indenyl] } zirconium dichloride; dimethylamidoboranebis 2-n-butyl, 4-(2-isopropylphenyl)indenyl]} zirconium dichloride; dimethylamidoboranebis 1- 2-isobutyl, 4-(2-isopropylphenyl)indenyl] }zirconium dichloride; dimethylamidoboranebis 2-sec-butyl, 4-(2-isopropylphenyl)indenyl] } zirconium dichloride; dimethylamidoboranebis 2-tert-butyl, 4-(2-isopropylphenyl)indenyl] } zirconium dichloride; dimethylamidoboranebis 2-phenyl, 4-(2-isopropy lpheny l)indenyl] } zirconium dichloride; dimethylamidoboranebis 2-n-propyl, 4-(2-n-butylphenyl)indenyl]} zirconium dichloride; dimethylamidoboranebis 2-isopropyl, 4-(2-n-buty lphenyl)indenyl] } zirconium dichloride; dimethylamidoboranebis 2-n-butyl, 4-(2-n-buty lphenyl)indenyl] } zirconium dichloride; dimethylamidoboranebis 1- 2-isobutyl, 4-(2-n-butylphenyl)indenyl]} zirconium dichloride; dimethylamidoboranebis 1- 2-sec-butyl, 4-(2-n-butylphenyl)indenyl]} zirconium dichloride; dimethylamidoboranebis 2-tert-butyl, 4-(2-n-butylphenyl)indenyl] } zirconium dichloride; dimethylamidoboranebis 1- 2-phenyl, 4-(2-n-butylphenyl)indenyl]} zirconium dichloride; dimethylamidoboranebis 1- 2-n-propyl, 4-(2-isobutylphenyl)indenyl]} zirconium dichloride; dimethylamidoboranebis 1- 2-isopropyl, 4-(2-isobutylphenyl)indenyl]} zirconium dichloride; dimethylamidoboranebis 1- 2-n-butyl, 4-(2-isobutylphenyl)indenyl] } zirconium dichloride; dimethylamidoboranebis 1- 2-isobutyl, 4-(2-isobutylphenyl)indenyl]} zirconium dichloride; dimethylamidoboranebis 2-sec-butyl, 4-(2-isobutylphenyl)indenyl]} zirconium dichloride; dimethylamidoboranebis 2-tert-butyl, 4-(2-isobutylphenyl)indenyl]} zirconium dichloride; dimethylamidoboranebis 2-phenyl, 4-(2-isobutylphenyl)indenyl] } zirconium dichloride; dimethylamidoboranebis 2-n-propyl, 4-(2-sec-butylphenyl)indenyl]} zirconium dichloride; dimethylamidoboranebis 2-isopropyl, 4-(2-sec-butylphenyl)indenyl] } zirconium dichloride; dimethylamidoboranebis 2-n-butyl, 4-(2-sec-butylphenyl)indenyl] } zirconium dichloride; dimethylamidoboranebis 2-isobutyl, 4-(2-sec-butylphenyl)indenyl] } zirconium dichloride; dimethylamidoboranebis 2-sec-butyl, 4-(2-sec-butylphenyl)indenyl] } zirconium dichloride; dimethylamidoboranebis 1- 2-tert-butyl, 4-(2-sec-butylphenyl)indenyl] } zirconium dichloride; dimethylamidoboranebis 1- 2-phenyl, 4-(2-sec-butylphenyl)indenyl] } zirconium dichloride; dimethylamidoboranebis 1- 2-n-propyl, 4-(2-tert-butylphenyl)indenyl] } zirconium dichloride; dimethylamidoboranebis 2-isopropyl, 4-(2-tert-butylphenyl)indenyl] } zirconium dichloride; dimethylamidoboranebis 1- 2-n-butyl, 4-(2 -tert-buty lpheny l)indeny 1] } zirconium dichloride; dimethylamidoboranebis 1- 2-isobutyl, 4-(2-tert-butylphenyl)indeny 1] } zirconium dichloride; dimethylamidoboranebis 1- 2-sec-butyl, 4-(2-tert-butylphenyl)indenyl]} zirconium dichloride; dimethylamidoboranebis 1- 2-tert-butyl, 4-(2-tert-butylphenyl)indenyl] } zirconium dichloride; dimethylamidoboranebis 1- 2-phenyl, 4-(2 -tert-buty lphenyl)indenyl]} zirconium dichloride; dimethylamidoboranebis 1- 2-n-propyl, 4-(2-biphenyl)indenyl] } zirconium dichloride; dimethylamidoboranebis 1- 2-isopropyl, 4-(2-biphenyl)indeny 1] } zirconium dichloride; dimethylamidoboranebis 1- 2-n-butyl, 4-(2-biphenyl)indenyl] } zirconium dichloride; dimethylamidoboranebis 1- 2-isobutyl, 4-(2-biphenyl)indenyl]} zirconium dichloride; dimethylamidoboranebis 1- 2-sec-butyl, 4-(2-biphenyl)indenyl]} zirconium dichloride; dimethylamidoboranebis 1- 2-tert-butyl, 4-(2-biphenyl)indeny 1] } zirconium dichloride; dimethylamidoboranebis 1- 2-phenyl, 4-(2-biphenyl)indeny 1] } zirconium dichloride; dimethylamidoboranebis 1- 2-n-propyl, 4-(2- -naphthylphenyl)indenyl] } zirconium dichloride; dimethy lamidoboranebi s 1- 2-isopropyl, 4-(2-α-naphthylpheny l)indenyl] } zirconium dichloride; dimethy lamidoboranebi s 1- 2-n-butyl, 4-(2-α-naphthylphenyl)indenyl]} zirconium dichloride; dimethy lamidoboranebi s 1- 2-isobutyl, 4-(2-α-naphthy lpheny l)indenyl] } zirconium dichloride; dimethylamidoboranebis 2-sec-butyl, 4-(2-α-naphthylphenyl)indenyl] } zirconium dichloride; dimethylamidoboranebis 1- 2-tert-butyl, 4-(2-α-naphthy lpheny l)indenyl] } zirconium dichloride; dimethylamidoboranebis 1- 2-phenyl, 4-(2-α-naphthylphenyl)indenyl]} zirconium dichloride; dimethylamidoboranebis 1- 2-n-propyl, 4-(2-β-naphthylpheny l)indeny 1] } zirconium dichloride; dimethylamidoboranebis 1- 2-isopropyl, 4-(2-β-naphthy lpheny l)indenyl] } zirconium dichloride; dimethylamidoboranebis 2-n-butyl, 4-(2-β-naphthy lpheny l)indenyl]} zirconium dichloride; dimethylamidoboranebis 1- 2-isobutyl, 4-(2-β-naphthy lpheny l)indenyl]} zirconium dichloride; dimethylamidoboranebis 1- 2-sec-butyl, 4-(2-β-naphthylphenyl)indenyl] } zirconium dichloride; dimethylamidoboranebis 1- 2-tert-butyl, 4-(2-β-naphthy lpheny l)indenyl] } zirconium dichloride; dimethylamidoboranebis 2-phenyl, 4-(2-β-naphthylphenyl)indenyl]} zirconium dichloride; dimethylamidoboranebis 2-n-propyl, 4-(2 -trifluoromethy lphenyl)indenyl] } - zirconium dichloride; dimethylamidoboranebis 2-isopropyl, 4-(2-trifluoromethylphenyl)indenyl] }- zirconium dichloride; dimethylamidoboranebis 1- 2-n-butyl, 4-(2 -trifluoromethy lpheny l)indeny 1] } - zirconium dichloride; dimethylamidoboranebis 1- 2-isobutyl, 4-(2 -trifluoromethy lpheny l)indenyl] } - zirconium dichloride; dimethylamidoboranebis 1- 2-sec-butyl, 4-(2-trifluoromethylphenyl)indenyl]}- zirconium dichloride; dimethylamidoboranebis 1- 2-tert-butyl, 4-(2 -trifluoromethy lphenyl)indenyl] } - zirconium dichloride; dimethylamidoboranebis 2 -phenyl, 4-(2 -trifluoromethy lphenyl)indenyl] }- zirconium dichloride; dimethylamidoboranebis 1- 2-n-propyl, 4-(2,3-dimethylphenyl)indenyl]} zirconium dichloride; dimethylamidoboranebis 2-isopropyl, 4-(2,3-dimethylphenyl)indenyl] } zirconium dichloride; dimethylamidoboranebis 2-n-butyl, 4-(2,3-dimethylphenyl)indenyl] }zirconium dichloride; dimethylamidoboranebis 2-isobutyl, 4-(2,3-dimethylphenyl)indenyl]} zirconium dichloride; dimethylamidoboranebis 1- 2-sec-butyl, 4-(2,3-dimethylphenyl)indenyl]} zirconium dichloride; dimethylamidoboranebis 2-tert-butyl, 4-(2,3-dimethylphenyl)indenyl] } zirconium dichloride; dimethylamidoboranebis 2-phenyl, 4-(2,3-dimethylphenyl)indenyl]}zirconium dichloride; dimethylamidoboranebis 1- 2-n-propyl, 4-(2,3 ,4-trimethylphenyl)indenyl] } zirconium dichloride; dimethylamidoboranebis 1- 2-isopropyl, 4-(2,3,4-trimethylphenyl)indenyl]} zirconium dichloride; dimethylamidoboranebis 1- 2-n-butyl, 4-(2,3,4-trimethylphenyl)indenyl]} zirconium dichloride; dimethylamidoboranebis 1- 2-isobutyl, 4-(2,3,4-trimethylphenyl)indenyl]} zirconium dichloride; dimethylamidoboranebis 1- 2-sec-butyl, 4-(2,3,4-trimethylphenyl)indenyl]} zirconium dichloride; dimethylamidoboranebis 1- 2-tert-butyl, 4-(2,3 ,4-trimethylphenyl)indenyl] } zirconium dichloride; dimethylamidoboranebis 1- 2-phenyl, 4-(2,3,4-trimethylphenyl)indenyl] } zirconium dichloride; dimethylamidoboranebis 1- 2-n-propyl, 4-(2,3,5-trimethylphenyl)indenyl]} zirconium dichloride; dimethylamidoboranebis 1- 2-isopropyl, 4-(2,3,5-trimethylphenyl)indenyl]} zirconium dichloride; dimethylamidoboranebis 2-n-butyl, 4-(2,3,5-trimethylphenyl)indenyl]} zirconium dichloride; dimethylamidoboranebis 1- 2-isobutyl, 4-(2,3,5-trimethylphenyl)indenyl] } zirconium dichloride; dimethylamidoboranebis 2-sec-butyl, 4-(2,3,5-trimethylphenyl)indenyl]} zirconium dichloride; dimethylamidoboranebis 2-tert-butyl, 4-(2,3,5-trimethylphenyl)indenyl]} zirconium dichloride; dimethylamidoboranebis 2-phenyl, 4-(2,3,5-trimethylphenyl)indenyl]} zirconium dichloride; dimethylamidoboranebis 1- 2-n-propyl, 4-(2-methylphenyl)indenyl]} zirconium dimethyl; dimethylamidoboranebis 1- 2-isopropyl, 4-(2-methy lpheny l)indeny 1] } zirconium dimethyl; dimethylamidoboranebis 2-n-butyl, 4-(2-methy lpheny l)indenyl] } zirconium dimethyl; dimethylamidoboranebis 2-isobutyl, 4-(2-methylpheny l)indenyl] } zirconium dimethyl; dimethylamidoboranebis 2-sec-butyl, 4-(2-methylphenyl)indenyl]} zirconium dimethyl; dimethylamidoboranebis 2-tert-butyl, 4-(2-methylphenyl)indenyl] } zirconium dimethyl; dimethylamidoboranebis 1- 2-phenyl, 4-(2-methylphenyl)indenyl]} zirconium dimethyl; dimethylamidoboranebis 1- 2-n-propyl, 4-(2-ethylphenyl)indenyl]} zirconium dimethyl; dimethylamidoboranebis 2-isopropyl, 4-(2-ethylphenyl)indenyl] } zirconium dimethyl; dimethylamidoboranebis 2-n-butyl, 4-(2-ethylphenyl)indenyl] } zirconium dimethyl; dimethylamidoboranebis 1- 2-isobutyl, 4-(2-ethy lpheny l)indenyl]} zirconium dimethyl; dimethylamidoboranebis 1- 2-sec-butyl, 4-(2-ethylphenyl)indenyl] } zirconium dimethyl; dimethylamidoboranebis 1- 2-tert-butyl, 4-(2-ethylphenyl)indenyl] } zirconium dimethyl; dimethylamidoboranebis 2-phenyl, 4-(2-ethy lpheny l)indenyl] } zirconium dimethyl; dimethylamidoboranebis 1- 2-n-propyl, 4-(2 -n-propy lphenyl)indenyl] } zirconium dimethyl; dimethylamidoboranebis 1- 2-isopropyl, 4-(2-n-propy lpheny l)indenyl] } zirconium dimethyl; dimethy lamidoboranebi s 1- 2-n-butyl, 4-(2 -n-propy lphenyl)indenyl] } zirconium dimethyl; dimethylamidoboranebis 1- 2-isobutyl, 4-(2 -n-propy lphenyl)indenyl] } zirconium dimethyl; dimethylamidoboranebis 2-sec-butyl, 4-(2-n-propy lpheny l)indenyl] } zirconium dimethyl; dimethylamidoboranebis 2-tert-butyl, 4-(2 -n-propy lpheny l)indenyl] } zirconium dimethyl; dimethy lamidoboranebi s 2-phenyl, 4-(2 -n-propy lphenyl)indenyl] } zirconium dimethyl; dimethylamidoboranebis 2-n-propyl, 4-(2-isopropy lpheny l)indenyl] } zirconium dimethyl; dimethylamidoboranebis 2-isopropyl, 4-(2-isopropylphenyl)indenyl] } zirconium dimethyl; dimethylamidoboranebis 2-n-butyl, 4-(2-isopropy lpheny l)indenyl]} zirconium dimethyl; dimethylamidoboranebis 2-isobutyl, 4-(2-isopropylphenyl)indenyl] } zirconium dimethyl; dimethylamidoboranebis 1- 2-sec-butyl, 4-(2-isopropylphenyl)indenyl] } zirconium dimethyl; dimethylamidoboranebis 1- 2-tert-butyl, 4-(2-isopropylphenyl)indenyl] } zirconium dimethyl; dimethylamidoboranebis 1- 2-phenyl, 4-(2-isopropylphenyl)indenyl]}zirconium dimethyl; dimethylamidoboranebis 1- 2-n-propyl, 4-(2-n-buty lpheny l)indeny 1] } zirconium dimethyl; dimethylamidoboranebis 1- 2-isopropyl, 4-(2-n-butylphenyl)indenyl] } zirconium dimethyl; dimethylamidoboranebis 1- 2-n-butyl, 4-(2-n-butylphenyl)indenyl] } zirconium dimethyl; dimethylamidoboranebis 2-isobutyl, 4-(2-n-buty lphenyl)indenyl] } zirconium dimethyl; dimethylamidoboranebis 2-sec-butyl, 4-(2-n-butylphenyl)indenyl] } zirconium dimethyl; dimethylamidoboranebis 2-tert-butyl, 4-(2-n-butylphenyl)indenyl] } zirconium dimethyl; dimethylamidoboranebis 2-phenyl, 4-(2-n-butylphenyl)indenyl]} zirconium dimethyl; dimethylamidoboranebis 2-n-propyl, 4-(2-isobutylphenyl)indenyl]} zirconium dimethyl; dimethylamidoboranebis 2-isopropyl, 4-(2-isobutylphenyl)indenyl]} zirconium dimethyl; dimethylamidoboranebis 2-n-butyl, 4-(2-isobuty lpheny l)indenyl]} zirconium dimethyl; dimethylamidoboranebis 2-isobutyl, 4-(2-isobutylphenyl)indenyl]} zirconium dimethyl; dimethylamidoboranebis 2-sec-butyl, 4-(2-isobutylphenyl)indenyl]}zirconium dimethyl; dimethylamidoboranebis 2-tert-butyl, 4-(2-isobutylphenyl)indenyl] } zirconium dimethyl; dimethylamidoboranebis 2-phenyl, 4-(2-isobutylphenyl)indenyl] } zirconium dimethyl; dimethylamidoboranebis 1- 2-n-propyl, 4-(2-sec-buty lpheny l)indeny 1] } zirconium dimethyl; dimethylamidoboranebis 2-isopropyl, 4-(2-sec-butylphenyl)indenyl]} zirconium dimethyl; dimethylamidoboranebis 1- 2-n-butyl, 4-(2-sec-butylphenyl)indenyl] } zirconium dimethyl; dimethylamidoboranebis 1- 2-isobutyl, 4-(2-sec-butylphenyl)indenyl]} zirconium dimethyl; dimethylamidoboranebis 1- 2-sec-butyl, 4-(2-sec-butylphenyl)indenyl] } zirconium dimethyl; dimethylamidoboranebis 2-tert-butyl, 4-(2-sec-butylphenyl)indenyl] } zirconium dimethyl; dimethylamidoboranebis 1- 2-phenyl, 4-(2-sec-butylphenyl)indenyl] } zirconium dimethyl; dimethylamidoboranebis 2-n-propyl, 4-(2-tert-butylphenyl)indenyl] } zirconium dimethyl; dimethylamidoboranebis 2-isopropyl, 4-(2-tert-butylphenyl)indenyl] } zirconium dimethyl; dimethy lamidoboranebi s 2-n-butyl, 4-(2-tert-butylphenyl)indenyl]} zirconium dimethyl; dimethylamidoboranebis 2-isobutyl, 4-(2 -tert-buty lphenyl)indenyl] } zirconium dimethyl; dimethylamidoboranebis 2-sec-butyl, 4-(2-tert-butylphenyl)indenyl] } zirconium dimethyl; dimethylamidoboranebis 1- 2-tert-butyl, 4-(2-tert-butylphenyl)indenyl] } zirconium dimethyl; dimethylamidoboranebi s 1- 2-phenyl, 4-(2-tert-butylphenyl)indenyl] } zirconium dimethyl; dimethylamidoboranebis 1- 2-n-propyl, 4-(2-biphenyl)indenyl]} zirconium dimethyl; dimethylamidoboranebis 2-isopropyl, 4-(2-biphenyl)indenyl] } zirconium dimethyl; dimethylamidoboranebis 2-n-butyl, 4-(2-biphenyl)indenyl] } zirconium dimethyl; dimethylamidoboranebis 2-isobutyl, 4-(2-bipheny l)indeny 1] } zirconium dimethyl; dimethylamidoboranebis 2-sec-butyl, 4-(2-biphenyl)indenyl] } zirconium dimethyl; dimethylamidoboranebis 2-tert-butyl, 4-(2-bipheny l)indenyl] } zirconium dimethyl; dimethylamidoboranebis 2-phenyl, 4-(2-biphenyl)indenyl] } zirconium dimethyl; dimethylamidoboranebis 2-n-propyl, 4-(2-α-naphthy lphenyl)indenyl] } zirconium dimethyl; dimethylamidoboranebis 2-isopropyl, 4-(2-α-naphthylphenyl)indenyl] } zirconium dimethyl; dimethylamidoboranebis 2-n-butyl, 4-(2-α-naphthylpheny l)indeny 1] } zirconium dimethyl; dimethylamidoboranebis 2-isobutyl, 4-(2-α-naphthylphenyl)indenyl] } zirconium dimethyl; dimethy lamidoboranebi s 2-sec-butyl, 4-(2-α-naphthy lpheny l)indenyl] } zirconium dimethyl; dimethylamidoboranebis 2-tert-butyl, 4-(2-α-naphthylphenyl)indenyl] } zirconium dimethyl; dimethylamidoboranebis 2-phenyl, 4-(2-α-naphthylphenyl)indenyl]} zirconium dimethyl; dimethylamidoboranebis 2-n-propyl, 4-(2-β-naphthylphenyl)indenyl] } zirconium dimethyl; dimethylamidoboranebis 2-isopropyl, 4-(2-β-naphthy lpheny l)indenyl] } zirconium dimethyl; dimethylamidoboranebis 2-n-butyl, 4-(2-β-naphthy lpheny l)indenyl]} zirconium dimethyl; dimethylamidoboranebis 2-isobutyl, 4-(2-β-naphthy lpheny l)indenyl] } zirconium dimethyl; dimethylamidoboranebis 1- 2-sec-butyl, 4-(2-β-naphthylphenyl)indenyl] } zirconium dimethyl; dimethylamidoboranebis 2-tert-butyl, 4-(2-β-naphthy lpheny l)indenyl] } zirconium dimethyl; dimethylamidoboranebis 2-phenyl, 4-(2-β-naphthy lpheny l)indenyl] } zirconium dimethyl; dimethylamidoboranebis 1- 2-n-propyl, 4-(2-trifluoromethylphenyl)indenyl] } - zirconium dimethyl; dimethylamidoboranebis 2-isopropyl, 4-(2-trifluoromethylphenyl)indenyl] } - zirconium dimethyl; dimethylamidoboranebis 1- 2-n-butyl, 4-(2-trifluoromethylphenyl)indenyl] } - zirconium dimethyl; dimethylamidoboranebis 2-isobutyl, 4-(2-trifluoromethylpheny l)indeny 1] } - zirconium dimethyl; dimethylamidoboranebis 2-sec-butyl, 4-(2 -trifluoromethy lphenyl)indenyl] } - zirconium dimethyl; dimethylamidoboranebis 2-tert-butyl, 4-(2-trifluoromethylphenyl)indenyl] } - zirconium dimethyl; dimethy lamidoboranebi s 1- 2-phenyl, 4-(2-trifluoromethylphenyl)indenyl] } - zirconium dimethyl; dimethylamidoboranebis 1- 2-n-propyl, 4-(2,3 -dimethy lpheny l)indenyl] } zirconium dimethyl; dimethylamidoboranebis 1- 2-isopropyl, 4-(2,3-dimethylphenyl)indenyl]} zirconium dimethyl; dimethylamidoboranebis 2-n-butyl, 4-(2,3-dimethylphenyl)indenyl] } zirconium dimethyl; dimethylamidoboranebis 2-isobutyl, 4-(2,3-dimethylphenyl)indenyl]} zirconium dimethyl; dimethylamidoboranebis 2-sec-butyl, 4-(2,3-dimethylphenyl)indenyl] } zirconium dimethyl; dimethylamidoboranebis 2-tert-butyl, 4-(2, 3 -dimethy lphenyl)indenyl]} zirconium dimethyl; dimethylamidoboranebis { 2-phenyl, 4-(2,3-dimethylphenyl)indenyl]}zirconium dimethyl; dimethylamidoboranebis { 2-n-propyl, 4-(2,3,4-trimethylphenyl)indenyl]} zirconium dimethyl; dimethylamidoboranebis { 2-isopropyl, 4-(2,3,4-trimethylphenyl)indenyl] } zirconium dimethyl; dimethylamidoboranebis { 2-n-butyl, 4-(2,3,4-trimethylphenyl)indenyl] } zirconium dimethyl; dimethylamidoboranebis ! 2-isobutyl, 4-(2,3,4-trimethylphenyl)indenyl]} zirconium dimethyl; dimethylamidoboranebis { 2-sec-butyl, 4-(2,3,4-trimethylphenyl)indenyl]} zirconium dimethyl; dimethylamidoboranebis { 2-tert-butyl, 4-(2,3,4-trimethylphenyl)indenyl] } zirconium dimethyl; dimethylamidoboranebis { 2-phenyl, 4-(2,3 ,4-trimethylphenyl)indenyl] } zirconium dimethyl; dimethylamidoboranebis ! 2-n-propyl, 4-(2,3,5-trimethylphenyl)indenyl]} zirconium dimethyl; dimethylamidoboranebis { 2-isopropyl, 4-(2,3,5-trimethylphenyl)indenyl]} zirconium dimethyl; dimethylamidoboranebis ! 2-n-butyl, 4-(2,3, 5 -trimethy lphenyl)indenyl]} zirconium dimethyl; dimethylamidoboranebis ! 2-isobutyl, 4-(2,3,5-trimethylphenyl)indenyl]} zirconium dimethyl; dimethylamidoboranebis { 2-sec-butyl, 4-(2, 3, 5 -trimethy lpheny l)indenyl]} zirconium dimethyl; dimethylamidoboranebis { 2-tert-butyl, 4-(2,3,5-trimethylphenyl)indenyl]} zirconium dimethyl; dimethylamidoboranebis! 2-phenyl, 4-(2,3,5-trimethylphenyl)indenyl]} zirconium dimethyl; dimethylamidoboranebis { 2-n-propyl, 4-(2-methylphenyl)indenyl]}hafnium dichloride; dimethylamidoboranebis 1- 2-isopropyl, 4-(2-methy lpheny l)indenyl]} hafnium dichloride; dimethylamidoboranebis 1- 2-n-butyl, 4-(2-methylphenyl)indenyl] } hafnium dichloride; dimethylamidoboranebis 2-isobutyl, 4-(2-methylphenyl)indenyl]} hafnium dichloride; dimethylamidoboranebis 1- 2-sec-butyl, 4-(2-methylphenyl)indenyl] }hafnium dichloride; dimethylamidoboranebis 2-tert-butyl, 4-(2-methylphenyl)indenyl] } hafnium dichloride; dimethylamidoboranebis 1- 2-phenyl, 4-(2-methylphenyl)indenyl] } hafnium dichloride; dimethylamidoboranebis 1- 2-n-propyl, 4-(2-ethylphenyl)indenyl] }hafnium dichloride; dimethylamidoboranebis 2-isopropyl, 4-(2-ethylphenyl)indenyl]}hafnium dichloride; dimethylamidoboranebis 2-n-butyl, 4-(2-ethylphenyl)indenyl] } hafnium dichloride; dimethylamidoboranebis 2-isobutyl, 4-(2-ethy lpheny l)indeny 1] } hafnium dichloride; dimethylamidoboranebis 2-sec-butyl, 4-(2-ethylphenyl)indenyl]}hafnium dichloride; dimethylamidoboranebis 2-tert-butyl, 4-(2-ethy lpheny l)indenyl] } hafnium dichloride; dimethylamidoboranebis 2-phenyl, 4-(2-ethylphenyl)indenyl] } hafnium dichloride; dimethylamidoboranebis 2-n-propyl, 4-(2-n-propylphenyl)indenyl]} hafnium dichloride; dimethylamidoboranebis 2-isopropyl, 4-(2-n-propylphenyl)indenyl]} hafnium dichloride; dimethylamidoboranebis 1- 2-n-butyl, 4-(2-n-propy lpheny l)indenyl] } hafnium dichloride; dimethylamidoboranebis 1- 2-isobutyl, 4-(2-n-propylphenyl)indenyl]} hafnium dichloride; dimethylamidoboranebis 1- 2-sec-butyl, 4-(2-n-propylphenyl)indenyl]}hafnium dichloride; dimethylamidoboranebis 1- 2-tert-butyl, 4-(2-n-propylphenyl)indenyl] } hafnium dichloride; dimethylamidoboranebis 1- 2-phenyl, 4-(2-n-propylphenyl)indenyl] } hafnium dichloride; dimethylamidoboranebis 1- 2-n-propyl, 4-(2-isopropylphenyl)indenyl] } hafnium dichloride; dimethylamidoboranebis 1- 2-isopropyl, 4-(2-isopropylphenyl)indenyl] } hafnium dichloride; dimethylamidoboranebis 1- 2-n-butyl, 4-(2-isopropylphenyl)indeny 1] } hafnium dichloride; dimethylamidoboranebis 1- 2-isobutyl, 4-(2-isopropy lpheny l)indenyl] } hafnium dichloride; dimethylamidoboranebis 1- 2-sec-butyl, 4-(2-isopropylphenyl)indenyl] } hafnium dichloride; dimethylamidoboranebis 1- 2-tert-butyl, 4-(2-isopropylphenyl)indenyl]} hafnium dichloride; dimethylamidoboranebis 1- 2-phenyl, 4-(2-isopropylphenyl)indenyl] } hafnium dichloride; dimethylamidoboranebis 1- 2-n-propyl, 4-(2-n-butylphenyl)indenyl] } hafnium dichloride; dimethylamidoboranebis 1- 2-isopropyl, 4-(2-n-butylphenyl)indenyl] }hafnium dichloride; dimethylamidoboranebis 2-n-butyl, 4-(2-n-butylphenyl)indenyl] } hafnium dichloride; dimethylamidoboranebis 1- 2-isobutyl, 4-(2-n-butylphenyl)indenyl] } hafnium dichloride; dimethylamidoboranebis 2-sec-butyl, 4-(2-n-butylphenyl)indenyl]} hafnium dichloride; dimethy lamidoboranebi s 2-tert-butyl, 4-(2-n-buty lpheny l)indenyl] } hafnium dichloride; dimethylamidoboranebis 2-phenyl, 4-(2-n-buty lpheny l)indeny 1] } hafnium dichloride; dimethylamidoboranebis 2-n-propyl, 4-(2-isobutylphenyl)indenyl] } hafnium dichloride; dimethylamidoboranebis 2-isopropyl, 4-(2-isobutylphenyl)indenyl]} hafnium dichloride; dimethylamidoboranebis 2-n-butyl, 4-(2-isobutylphenyl)indenyl] } hafnium dichloride; dimethylamidoboranebis 2-isobutyl, 4-(2-isobutylphenyl)indenyl]} hafnium dichloride; dimethylamidoboranebis 2-sec-butyl, 4-(2-isobutylphenyl)indenyl]} hafnium dichloride; dimethylamidoboranebis 2-tert-butyl, 4-(2-isobuty lpheny l)indenyl] } hafnium dichloride; dimethylamidoboranebis 2-phenyl, 4-(2-isobutylphenyl)indenyl]} hafnium dichloride; dimethylamidoboranebis 2-n-propyl, 4-(2-sec-butylphenyl)indenyl] }hafnium dichloride; dimethylamidoboranebis 2-isopropyl, 4-(2-sec-buty lpheny l)indenyl]} hafnium dichloride; dimethylamidoboranebis 2-n-butyl, 4-(2-sec-butylphenyl)indenyl] } hafnium dichloride; dimethylamidoboranebis 2-isobutyl, 4-(2-sec-butylphenyl)indenyl]} hafnium dichloride; dimethylamidoboranebis 2-sec-butyl, 4-(2-sec-butylphenyl)indenyl] }hafnium dichloride; dimethylamidoboranebis 2-tert-butyl, 4-(2-sec-butylphenyl)indenyl]} hafnium dichloride; dimethylamidoboranebis 2-phenyl, 4-(2-sec-butylphenyl)indenyl]} hafnium dichloride; dimethylamidoboranebis 2-n-propyl, 4-(2-tert-butylphenyl)indenyl]} hafnium dichloride; dimethylamidoboranebis 2-isopropyl, 4-(2-tert-butylphenyl)indenyl] } hafnium dichloride; dimethylamidoboranebis 2-n-butyl, 4-(2-tert-buty lpheny l)indenyl] } hafnium dichloride; dimethylamidoboranebis 2-isobutyl, 4-(2-tert-butylphenyl)indenyl] } hafnium dichloride; dimethylamidoboranebis 2-sec-butyl, 4-(2-tert-butylpheny l)indenyl] } hafnium dichloride; dimethylamidoboranebis 2-tert-butyl, 4-(2-tert-butylphenyl)indenyl] } hafnium dichloride; dimethylamidoboranebis 2-phenyl, 4-(2 -tert-buty lpheny l)indenyl] } hafnium dichloride; dimethylamidoboranebis 2-n-propyl, 4-(2-bipheny l)indeny 1] } hafnium dichloride; dimethylamidoboranebis 2-isopropyl, 4-(2-biphenyl)indenyl]} hafnium dichloride; dimethylamidoboranebis 2-n-butyl, 4-(2-biphenyl)indenyl] } hafnium dichloride; dimethylamidoboranebis 2-isobutyl, 4-(2-biphenyl)indenyl] } hafnium dichloride; dimethylamidoboranebis 2-sec-butyl, 4-(2-biphenyl)indenyl]}hafnium dichloride; dimethylamidoboranebis 2-tert-butyl, 4-(2-biphenyl)indenyl] } hafnium dichloride; dimethylamidoboranebis 2-phenyl, 4-(2-biphenyl)indenyl] } hafnium dichloride; dimethylamidoboranebis 2-n-propyl, 4-(2-α-naphthylphenyl)indenyl]} hafnium dichloride; dimethylamidoboranebis 2-isopropyl, 4-(2-α-naphthylphenyl)indenyl] } hafnium dichloride; dimethylamidoboranebis! 2-n-butyl, 4-(2-α-naphthy lpheny l)indeny 1] } hafnium dichloride; dimethylamidoboranebis! 2-isobutyl, 4-(2-α-naphthylphenyl)indenyl]}hafnium dichloride; dimethylamidoboranebis ! 2-sec-butyl, 4-(2-α-naphthylphenyl)indenyl] } hafnium dichloride; dimethylamidoboranebis ! 2-tert-butyl, 4-(2-α-naphthylphenyl)indenyl] } hafnium dichloride; dimethylamidoboranebis! 2-phenyl, 4-(2-α-naphthy lpheny l)indenyl] } hafnium dichloride; dimethylamidoboranebis { 2-n-propyl, 4-(2-β-naphthylphenyl)indenyl] }hafnium dichloride; dimethylamidoboranebis { 2-isopropyl, 4-(2-β-naphthy lpheny l)indenyl] } hafnium dichloride; dimethylamidoboranebis { 2-n-butyl, 4-(2-β-naphthylphenyl)indenyl] }hafnium dichloride; dimethylamidoboranebis ! 2-isobutyl, 4-(2-β-naphthy lpheny l)indenyl]} hafnium dichloride; dimethylamidoboranebis { 2-sec-butyl, 4-(2-β-naphthylphenyl)indenyl] } hafnium dichloride; dimethylamidoboranebis { 2-tert-butyl, 4-(2-β-naphthylphenyl)indenyl] } hafnium dichloride; dimethylamidoboranebis! 2-phenyl, 4-(2-β-naphthylphenyl)indenyl]} hafnium dichloride; dimethylamidoboranebis { 2-n-propyl, 4-(2-trifluoromethylphenyl)indenyl] } - hafnium dichloride; dimethylamidoboranebis! 2-isopropyl, 4-(2-trifluoromethylphenyl)indenyl] } ■ hafnium dichloride; dimethylamidoboranebis! 2-n-butyl, 4-(2-trifluoromethy lphenyl)indeny 1] } - hafnium dichloride; dimethylamidoboranebis { 2-isobutyl, 4-(2-trifluoromethylphenyl)indenyl] } - hafnium dichloride; dimethylamidoboranebis { 2-sec-butyl, 4-(2 -trifluoromethy lphenyl)indenyl] }- hafnium dichloride; dimethylamidoboranebis { 2-tert-butyl, 4-(2-trifluoromethy lpheny l)indenyl] }- hafnium dichloride; dimethylamidoboranebis { 2-phenyl, 4-(2-trifluoromethylphenyl)indenyl] } - hafnium dichloride; dimethylamidoboranebis { 2-n-propyl, 4-(2,3-dimethylphenyl)indenyl]}hafnium dichloride; dimethylamidoboranebis { 2-isopropyl, 4-(2,3-dimethylphenyl)indenyl] } hafnium dichloride; dimethylamidoboranebis! 2-n-butyl, 4-(2,3-dimethylphenyl)indenyl] }hafnium dichloride; dimethylamidoboranebis { 2-isobutyl, 4-(2,3-dimethylphenyl)indenyl] }hafnium dichloride; dimethylamidoboranebis { 2-sec-butyl, 4-(2,3-dimethylphenyl)indenyl]} hafnium dichloride; dimethylamidoboranebis ! 2-tert-butyl, 4-(2,3-dimethylphenyl)indenyl] } hafnium dichloride; dimethylamidoboranebis! 2-phenyl, 4-(2,3-dimethylphenyl)indenyl]}hafnium dichloride; dimethylamidoboranebis ! 2-n-propyl, 4-(2,3,4-trimethylphenyl)indenyl]} hafnium dichloride; dimethylamidoboranebis { 2-isopropyl, 4-(2,3,4-trimethylphenyl)indenyl]} hafnium dichloride; dimethylamidoboranebis ! 2-n-butyl, 4-(2,3 ,4-trimethylphenyl)indenyl] } hafnium dichloride; dimethylamidoboranebis! 2-isobutyl, 4-(2,3,4-trimethylphenyl)indenyl] } hafnium dichloride; dimethylamidoboranebis { 2-sec-butyl, 4-(2,3,4-trimethylphenyl)indenyl]} hafnium dichloride; dimethylamidoboranebis { 2-tert-butyl, 4-(2, 3, 4-trimethy lphenyl)indenyl]} hafnium dichloride; dimethylamidoboranebis 2-phenyl, 4-(2,3,4-trimethylphenyl)indenyl]} hafnium dichloride; dimethylamidoboranebis 2-n-propyl, 4-(2, 3, 5 -trimethy lphenyl)indenyl]} hafnium dichloride; dimethylamidoboranebis 2-isopropyl, 4-(2,3,5-trimethylphenyl)indenyl]} hafnium dichloride; dimethylamidoboranebis 2-n-butyl, 4-(2,3,5-trimethylphenyl)indenyl]} hafnium dichloride; dimethylamidoboranebis 2-isobutyl, 4-(2,3,5-trimethylphenyl)indenyl]} hafnium dichloride; dimethylamidoboranebis 2-sec-butyl, 4-(2,3,5-trimethylphenyl)indenyl]} hafnium dichloride; dimethylamidoboranebis 2-tert-butyl, 4-(2,3,5-trimethylphenyl)indenyl] } hafnium dichloride; dimethylamidoboranebis 2-phenyl, 4-(2,3,5-trimethylphenyl)indenyl]}hafnium dichloride; dimethylamidoboranebis 2-n-propyl, 4-(2-methylphenyl)indenyl] } hafnium dimethyl; dimethylamidoboranebis 2-isopropyl, 4-(2-methylphenyl)indenyl]} hafnium dimethyl; dimethylamidoboranebis 2-n-butyl, 4-(2-methylphenyl)indenyl] } hafnium dimethyl; dimethylamidoboranebis 2-isobutyl, 4-(2 -methy lpheny l)indenyl]} hafnium dimethyl; dimethylamidoboranebis 2-sec-butyl, 4-(2-methylphenyl)indenyl]} hafnium dimethyl; dimethylamidoboranebis 2-tert-butyl, 4-(2-methy lpheny l)indenyl]} hafnium dimethyl; dimethylamidoboranebis 2-phenyl, 4-(2-methylphenyl)indenyl] } hafnium dimethyl; dimethylamidoboranebis 2-n-propyl, 4-(2-ethylphenyl)indenyl] }hafnium dimethyl; dimethylamidoboranebis 1- 2-isopropyl, 4-(2-ethy lpheny l)indeny 1] } hafnium dimethyl; dimethylamidoboranebis 1- 2-n-butyl, 4-(2-ethy lpheny l)indeny 1] } hafnium dimethyl; dimethy lamidoboranebi s 1- 2-isobutyl, 4-(2-ethylphenyl)indenyl] }hafnium dimethyl; dimethylamidoboranebis 2-sec-butyl, 4-(2-ethylphenyl)indeny 1] } hafnium dimethyl; dimethy lamidoboranebi s 2-tert-butyl, 4-(2-ethylphenyl)indenyl]} hafnium dimethyl; dimethylamidoboranebis 2-phenyl, 4-(2-ethy lpheny l)indenyl] } hafnium dimethyl; dimethylamidoboranebis 1- 2-n-propyl, 4-(2-n-propy lpheny l)indeny 1] } hafnium dimethyl; dimethylamidoboranebis 1- 2-isopropyl, 4-(2-n-propylphenyl)indenyl]} hafnium dimethyl; dimethylamidoboranebis 1- 2-n-butyl, 4-(2-n-propylphenyl)indenyl] }hafnium dimethyl; dimethylamidoboranebis 1- 2-isobutyl, 4-(2-n-propylphenyl)indenyl]} hafnium dimethyl; dimethylamidoboranebis 1- 2-sec-butyl, 4-(2-n-propylphenyl)indenyl] } hafnium dimethyl; dimethylamidoboranebis 1- 2-tert-butyl, 4-(2-n-propylphenyl)indenyl]} hafnium dimethyl; dimethylamidoboranebis 1- 2-phenyl, 4-(2-n-propy lpheny l)indenyl]} hafnium dimethyl; dimethylamidoboranebis 1- 2-n-propyl, 4-(2-isopropylphenyl)indenyl] }hafnium dimethyl; dimethylamidoboranebis 1- 2-isopropyl, 4-(2-isopropylphenyl)indenyl] }hafnium dimethyl; dimethylamidoboranebis 2-n-butyl, 4-(2-isopropy lpheny l)indenyl]} hafnium dimethyl; dimethylamidoboranebis 1- 2-isobutyl, 4-(2-isopropylphenyl)indenyl] } hafnium dimethyl; dimethylamidoboranebis 1- 2-sec-butyl, 4-(2-isopropylphenyl)indenyl]}hafnium dimethyl; dimethy lamidoboranebi s 2-tert-butyl, 4-(2-isopropy lpheny l)indenyl]} hafnium dimethyl; dimethylamidoboranebis 1- 2-phenyl, 4-(2-isopropylphenyl)indenyl] }hafnium dimethyl; dimethy lamidoboranebi s 1- 2-n-propyl, 4-(2-n-butylphenyl)indenyl] } hafnium dimethyl; dimethylamidoboranebis 1- 2-isopropyl, 4-(2-n-butylphenyl)indenyl] } hafnium dimethyl; dimethylamidoboranebis 1- 2-n-butyl, 4-(2-n-buty lpheny l)indeny 1] } hafnium dimethyl; dimethylamidoboranebis 2-isobutyl, 4-(2-n -buty lpheny l)indenyl] } hafnium dimethyl; dimethy lamidoboranebi s 2-sec-butyl, 4-(2-n-butylphenyl)indenyl]} hafnium dimethyl; dimethylamidoboranebis 2-tert-butyl, 4-(2-n-butylphenyl)indenyl] } hafnium dimethyl; dimethylamidoboranebis 2-phenyl, 4-(2-n-butylphenyl)indenyl] }hafnium dimethyl; dimethylamidoboranebis 2-n-propyl, 4-(2-isobutylphenyl)indenyl] }hafnium dimethyl; dimethylamidoboranebis 2-isopropyl, 4-(2-isobutylphenyl)indenyl]} hafnium dimethyl; dimethylamidoboranebis 2-n-butyl, 4-(2-isobutylphenyl)indenyl]} hafnium dimethyl; dimethylamidoboranebis 2-isobutyl, 4-(2-isobutylphenyl)indenyl]} hafnium dimethyl; dimethylamidoboranebis 1- 2-sec-butyl, 4-(2-isobutylphenyl)indenyl]} hafnium dimethyl; dimethylamidoboranebis 2-tert-butyl, 4-(2-isobuty lpheny l)indenyl]} hafnium dimethyl; dimethylamidoboranebis 2-phenyl, 4-(2-isobutylphenyl)indenyl]} hafnium dimethyl; dimethylamidoboranebis 2-n-propyl, 4-(2-sec-butylphenyl)indenyl] } hafnium dimethyl; dimethylamidoboranebis 1- 2-isopropyl, 4-(2-sec-buty lpheny l)indenyl]} hafnium dimethyl; dimethylamidoboranebis 1- 2-n-butyl, 4-(2-sec-butylphenyl)indenyl] } hafnium dimethyl; dimethylamidoboranebis 1- 2-isobutyl, 4-(2-sec-buty lpheny l)indeny 1] } hafnium dimethyl; dimethy lamidoboranebi s 1- 2-sec-butyl, 4-(2-sec-butylphenyl)indenyl]}hafnium dimethyl; dimethylamidoboranebis 2-tert-butyl, 4-(2-sec-butylphenyl)indenyl] } hafnium dimethyl; dimethylamidoboranebis 2-phenyl, 4-(2-sec-butylphenyl)indenyl]} hafnium dimethyl; dimethylamidoboranebis 2-n-propyl, 4-(2-tert-butylphenyl)indenyl]}hafnium dimethyl; dimethylamidoboranebis 2-isopropyl, 4-(2-tert-butylphenyl)indenyl]} hafnium dimethyl; dimethylamidoboranebis 2-n-butyl, 4-(2-tert-butylphenyl)indenyl]} hafnium dimethyl; dimethylamidoboranebis 2-isobutyl, 4-(2-tert-butylphenyl)indenyl] } hafnium dimethyl; dimethylamidoboranebis 1- 2-sec-butyl, 4-(2-tert-buty lpheny l)indenyl]} hafnium dimethyl; dimethylamidoboranebis 1- 2-tert-butyl, 4-(2-tert-buty lpheny l)indenyl] } hafnium dimethyl; dimethy lamidoboranebi s 1- 2-phenyl, 4-(2 -tert-buty lphenyl)indenyl] } hafnium dimethyl; dimethylamidoboranebis { 2-n-propyl, 4-(2-biphenyl)indenyl]}hafnium dimethyl; dimethylamidoboranebis { 2-isopropyl, 4-(2-biphenyl)indenyl] } hafnium dimethyl; dimethylamidoboranebis { 2-n-butyl, 4-(2-biphenyl)indenyl]}hafnium dimethyl; dimethylamidoboranebis! 2-isobutyl, 4-(2-biphenyl)indenyl]} hafnium dimethyl; dimethylamidoboranebis { 2-sec-butyl, 4-(2-biphenyl)indenyl] } hafnium dimethyl; dimethylamidoboranebis { 2-tert-butyl, 4-(2-biphenyl)indenyl] } hafnium dimethyl; dimethylamidoboranebis ! 2-phenyl, 4-(2-biphenyl)indenyl]} hafnium dimethyl; dimethylamidoboranebis { 2-n-propyl, 4-(2-α-naphthy lpheny l)indenyl]} hafnium dimethyl; dimethylamidoboranebis ! 2-isopropyl, 4-(2-α-naphthylphenyl)indenyl] } hafnium dimethyl; dimethylamidoboranebis ! 2-n-butyl, 4-(2-α-naphthy lpheny l)indenyl] } hafnium dimethyl; dimethylamidoboranebis { 2-isobutyl, 4-(2-α-naphthy lpheny l)indenyl]} hafnium dimethyl; dimethylamidoboranebis { 2-sec-butyl, 4-(2-α-naphthylphenyl)indenyl] } hafnium dimethyl; dimethylamidoboranebis { 2-tert-butyl, 4-(2-α-naphthylphenyl)indenyl] } hafnium dimethyl; dimethylamidoboranebis { 2-phenyl, 4-(2-α-naphthylpheny l)indeny 1] } hafnium dimethyl; dimethylamidoboranebis { 2-n-propyl, 4-(2-β-naphthy lpheny l)indenyl]} hafnium dimethyl; dimethylamidoboranebis! 2-isopropyl, 4-(2-β-naphthylphenyl)indenyl] } hafnium dimethyl; dimethylamidoboranebis! 2-n-butyl, 4-(2-β-naphthylphenyl)indenyl] } hafnium dimethyl; dimethylamidoboranebis 1- 2-isobutyl, 4-(2-β-naphthylphenyl)indenyl] }hafnium dimethyl; dimethylamidoboranebis 2-sec-butyl, 4-(2-β-naphthy lpheny l)indenyl] } hafnium dimethyl; dimethylamidoboranebis 2-tert-butyl, 4-(2-β-naphthy lpheny l)indenyl] } hafnium dimethyl; dimethylamidoboranebis 1- 2-phenyl, 4-(2-β-naphthylphenyl)indenyl] jhafnium dimethyl; dimethylamidoboranebis 1- 2-n-propyl, 4-(2-trifluoromethylphenyl)indenyl] } - hafnium dimethyl; dimethylamidoboranebis 1- 2-isopropyl, 4-(2-trifluoromethylphenyl)indeny 1] } - hafnium dimethyl; dimethylamidoboranebis 1- 2-n-butyl, 4-(2-trifiuoromethylphenyl)indenyl] } ■ hafnium dimethyl; dimethylamidoboranebi s 1- 2-isobutyl, 4-(2-trifluoromethylphenyl)indenyl] } - hafnium dimethyl; dimethylamidoboranebis 2-sec-butyl, 4-(2-trifluoromethylphenyl)indenyl]}- hafnium dimethyl; dimethylamidoboranebis 2-tert-butyl, 4-(2-trifluoromethylphenyl)indenyl] } - hafnium dimethyl; dimethylamidoboranebis 2-phenyl, 4-(2-trifluoromethylphenyl)indenyl] } - hafnium dimethyl; dimethylamidoboranebis 2-n-propyl, 4-(2,3-dimethylphenyl)indenyl] }hafnium dimethyl; dimethylamidoboranebis 2-isopropyl, 4-(2,3-dimethylphenyl)indenyl]} hafnium dimethyl; dimethylamidoboranebis 2-n-butyl, 4-(2,3-dimethylphenyl)indenyl]}hafnium dimethyl; dimethylamidoboranebis 2-isobutyl, 4-(2,3-dimethylphenyl)indenyl]} hafnium dimethyl; dimethylamidoboranebis 1- 2-sec-butyl, 4-(2,3 -dimethylphenyl)indenyl] } hafnium dimethyl; dimethylamidoboranebis 2-tert-butyl, 4-(2,3-dimethylphenyl)indenyl] } hafnium dimethyl; dimethylamidoboranebis 2-phenyl, 4-(2,3-dimethylphenyl)indenyl]}hafnium dimethyl; dimethylamidoboranebis 2-n-propyl, 4-(2,3 ,4-trimethylphenyl)indenyl] } hafnium dimethyl; dimethylamidoboranebis 1- 2-isopropyl, 4-(2,3 ,4-trimethylphenyl)indenyl] } hafnium dimethyl; dimethylamidoboranebis 1- 2-n-butyl, 4-(2,3,4-trimethylphenyl)indenyl]} hafnium dimethyl ; dimethy lamidoboranebi s 1- 2-isobutyl, 4-(2,3 ,4-trimethylphenyl)indenyl] } hafnium dimethyl; dimethylamidoboranebis 1- 2-sec-butyl, 4-(2,3 ,4-trimethylphenyl)indenyl] } hafnium dimethyl; dimethylamidoboranebis 2-tert-butyl, 4-(2,3,4-trimethylphenyl)indenyl]} hafnium dimethyl; dimethylamidoboranebis 2-phenyl, 4-(2,3,4-trimethylphenyl)indenyl]} hafnium dimethyl; dimethylamidoboranebis 2-n-propyl, 4-(2,3,5-trimethylphenyl)indenyl] } hafnium dimethyl; dimethylamidoboranebis 2-isopropyl, 4-(2,3,5-trimethylphenyl)indenyl]} hafnium dimethyl; dimethylamidoboranebis 2-n-butyl, 4-(2,3,5-trimethylphenyl)indenyl] } hafnium dimethyl; dimethylamidoboranebis 2-isobutyl, 4-(2,3,5-trimethylphenyl)indenyl]} hafnium dimethyl; dimethylamidoboranebis 2-sec-butyl, 4-(2,3,5-trimethylphenyl)indenyl]} hafnium dimethyl; dimethylamidoboranebis 2-tert-butyl, 4-(2,3,5-trimethylphenyl)indenyl]} hafnium dimethyl; dimethylamidoboranebis 1- 2-phenyl, 4-(2,3,5-trimethylphenyl)indenyl]}hafnium dimethyl; diisopropylamidoboranebis 2-n-propyl, 4-(2-methylphenyl)indenyl]} hafnium dichloride; diisopropylamidoboranebis 2-isopropyl, 4-(2-methy lpheny l)indenyl] } hafnium dichloride; diisopropylamidoboranebis 2-n-butyl, 4-(2-methylphenyl)indenyl] } hafnium dichloride; diisopropylamidoboranebis 2-isobutyl, 4-(2-methylphenyl)indenyl] } hafnium dichloride; diisopropylamidoboranebis 2-sec-butyl, 4-(2-mefhylphenyl)indenyl]} hafnium dichloride; diisopropylamidoboranebis 2-tert-butyl, 4-(2-methylphenyl)indenyl] } hafnium dichloride; diisopropylamidoboranebis 1- 2-phenyl, 4-(2-methylphenyl)indenyl] } hafnium dichloride; diisopropylamidoboranebis 1- 2-n-propyl, 4-(2-ethylphenyl)indenyl]} hafnium dichloride; diisopropylamidoboranebis 1- 2-isopropyl, 4-(2-ethylphenyl)indenyl]} hafnium dichloride; diisopropylamidoboranebis 1- 2-n-butyl, 4-(2-ethylphenyl)indenyl] } hafnium dichloride; diisopropylamidoboranebis 1- 2-isobutyl, 4-(2-ethylphenyl)indenyl] }hafnium dichloride; diisopropylamidoboranebis 1- 2-sec-butyl, 4-(2-ethy lphenyl)indenyl] } hafnium dichloride; diisopropylamidoboranebis 2-tert-butyl, 4-(2-ethylphenyl)indenyl] } hafnium dichloride; diisopropylamidoboranebis 2-phenyl, 4-(2-ethylphenyl)indenyl]} hafnium dichloride; di i sopropy lamidoboranebi s 1- 2-n-propyl, 4-(2-n-propylphenyl)indenyl]} hafnium dichloride; diisopropylamidoboranebis 2-isopropyl, 4-(2-n-propylphenyl)indenyl] } hafnium dichloride; diisopropylamidoboranebis 2-n-butyl, 4-(2-n-propylphenyl)indenyl]} hafnium dichloride; diisopropylamidoboranebis 2-isobutyl, 4-(2-n-propy lpheny l)indenyl] } hafnium dichloride; diisopropylamidoboranebis 2-sec-butyl, 4-(2-n-propylphenyl)indenyl] } hafnium dichloride; diisopropylamidoboranebis 2-tert-butyl, 4-(2-n-propylphenyl)indenyl]hafnium dichloride; diisopropylamidoboranebis 2-phenyl, 4-(2-n-propylphenyl)indenyl] } hafnium dichloride; diisopropylamidoboranebis 1- 2-n-propyl, 4-(2-isopropylphenyl)indenyl] } hafnium dichloride; diisopropylamidoboranebis 1- 2-isopropyl, 4-(2-isopropylphenyl)indenyl] } hafnium dichloride; diisopropylamidoboranebis 1- 2-n-butyl, 4-(2-isopropylphenyl)indenyl]} hafnium dichloride; diisopropylamidoboranebis 1- 2-isobutyl, 4-(2-isopropylphenyl)indenyl] } hafnium dichloride; diisopropylamidoboranebis 2-sec-butyl, 4-(2-isopropylphenyl)indenyl] } hafnium dichloride; diisopropylamidoboranebis 2-tert-butyl, 4-(2-isopropylphenyl)indenyl] } hafnium dichloride; diisopropylamidoboranebis 2-phenyl, 4-(2-isopropylphenyl)indenyl] } hafnium dichloride; diisopropylamidoboranebis 1- 2-n-propyl, 4-(2-n-butylphenyl)indenyl]} hafnium dichloride; diisopropylamidoboranebis 2-isopropyl, 4-(2-n-buty lphenyl)indeny 1] } hafnium dichloride; diisopropylamidoboranebis 2-n-butyl, 4-(2-n-butylphenyl)indenyl] } hafnium dichloride; diisopropylamidoboranebis 2-isobutyl, 4-(2-n-butylphenyl)indenyl]} hafnium dichloride; diisopropylamidoboranebis 1- 2-sec-butyl, 4-(2-n-buty lpheny l)indenyl] } hafnium dichloride; diisopropylamidoboranebis 1- 2-tert-butyl, 4-(2 -n-buty lpheny l)indeny 1] } hafnium dichloride; diisopropylamidoboranebis 1- 2-phenyl, 4-(2-n-buty lpheny l)indenyl] } hafnium dichloride; diisopropylamidoboranebis 1- 2-n-propyl, 4-(2-isobutylphenyl)indenyl] }hafnium dichloride; diisopropylamidoboranebis 2-isopropyl, 4-(2-isobutylphenyl)indenyl] } hafnium dichloride; diisopropylamidoboranebis 2-n-butyl, 4-(2-isobuty lpheny l)indenyl] } hafnium dichloride; diisopropylamidoboranebis 1- 2-isobutyl, 4-(2-isobutylphenyl)indenyl]} hafnium dichloride; diisopropylamidoboranebis 2-sec-butyl, 4-(2-isobutylphenyl)indenyl]} hafnium dichloride; diisopropylamidoboranebis 2-tert-butyl, 4-(2-isobutylphenyl)indenyl] }hafnium dichloride; diisopropylamidoboranebis 2-phenyl, 4-(2-isobutylphenyl)indenyl] }hafnium dichloride; diisopropylamidoboranebis 2-n-propyl, 4-(2-sec-butylphenyl)indenyl] } hafnium dichloride; diisopropylamidoboranebis 2-isopropyl, 4-(2-sec-butylphenyl)indenyl] } hafnium dichloride; diisopropylamidoboranebis 2-n-butyl, 4-(2-sec-butylphenyl)indenyl]} hafnium dichloride; diisopropylamidoboranebis 2-isobutyl, 4-(2-sec-butylphenyl)indenyl] } hafnium dichloride; diisopropylamidoboranebis 2-sec-butyl, 4-(2-sec-butylphenyl)indenyl] } hafnium dichloride; diisopropylamidoboranebis 2-tert-butyl, 4-(2-sec-butylphenyl)indenyl] } hafnium dichloride; diisopropylamidoboranebis 2 -phenyl, 4-(2-sec-butylphenyl)indenyl] } hafnium dichloride; diisopropylamidoboranebis 1- 2-n-propyl, 4-(2-tert-butylphenyl)indenyl] } hafnium dichloride; diisopropylamidoboranebis 1- 2-isopropyl, 4-(2-tert-butylphenyl)indenyl] } hafnium dichloride; diisopropylamidoboranebis 2-n-butyl, 4-(2 -tert-buty lpheny l)indenyl] } hafnium dichloride; diisopropylamidoboranebis 1- 2-isobutyl, 4-(2-tert-butylphenyl)indenyl]} hafnium dichloride; diisopropylamidoboranebis 1- 2-sec-butyl, 4-(2-tert-butylphenyl)indenyl] } hafnium dichloride; diisopropylamidoboranebis 1- 2-tert-butyl, 4-(2-tert-butylphenyl)indenyl] } hafnium dichloride; diisopropylamidoboranebis 2-phenyl, 4-(2-tert-buty lpheny l)indenyl]} hafnium dichloride; diisopropylamidoboranebis 2-n-propyl, 4-(2-biphenyl)indenyl] } hafnium dichloride; diisopropylamidoboranebis 2-isopropyl, 4-(2-biphenyl)indenyl]} hafnium dichloride; diisopropylamidoboranebis 2-n-butyl, 4-(2-biphenyl)indenyl] } hafnium dichloride; diisopropylamidoboranebis 2-isobutyl, 4-(2-biphenyl)indenyl]} hafnium dichloride; diisopropylamidoboranebis 2-sec-butyl, 4-(2-biphenyl)indenyl]} hafnium dichloride; diisopropylamidoboranebis 2-tert-butyl, 4-(2-biphenyl)indenyl]} hafnium dichloride; diisopropylamidoboranebis 2-phenyl, 4-(2-bipheny l)indeny 1] } hafnium dichloride; diisopropylamidoboranebis 2-n-propyl, 4-(2-α-naphthylphenyl)indenyl] } hafnium dichloride; diisopropylamidoboranebis 2-isopropyl, 4-(2-α-naphthylphenyl)indenyl] } hafnium dichloride; diisopropylamidoboranebis 2-n-butyl, 4-(2-α-naphthylphenyl)indenyl] } hafnium dichloride; diisopropylamidoboranebis 2-isobutyl, 4-(2-α-naphthylphenyl)indenyl]} hafnium dichloride; diisopropylamidoboranebis 2-sec-butyl, 4-(2-α-naphthylphenyl)indenyl] } hafnium dichloride; diisopropylamidoboranebis 2-tert-butyl, 4-(2-α-naphthylphenyl)indenyl] } hafnium dichloride; diisopropylamidoboranebis 2-phenyl, 4-(2-α-naphthylphenyl)indenyl] } hafnium dichloride; diisopropylamidoboranebis 2-n-propyl, 4-(2-β-naphthylphenyl)indeny 1] } hafnium dichloride; diisopropylamidoboranebis 2-isopropyl, 4-(2-β-naphthy lpheny l)indenyl] } hafnium dichloride; diisopropylamidoboranebis 2-n-butyl, 4-(2-β-naphthylphenyl)indenyl] } hafnium dichloride; diisopropylamidoboranebis 2-isobutyl, 4-(2-β-naphthylphenyl)indenyl] } hafnium dichloride; diisopropylamidoboranebis 2-sec-butyl, 4-(2-β-naphthylphenyl)indenyl] } hafnium dichloride; diisopropylamidoboranebis 2-tert-butyl, 4-(2-β-naphthylphenyl)indenyl] } hafnium dichloride; diisopropylamidoboranebis 2-phenyl, 4-(2-β-naphthylphenyl)indenyl] } hafnium dichloride; diisopropylamidoboranebis 2-n-propyl, 4-(2-trifluoromethylphenyl)indenyl] } - hafnium dichloride; diisopropylamidoboranebis 2-isopropyl, 4-(2-trifluoromethylphenyl)indenyl] }- hafnium dichloride; diisopropylamidoboranebis 2-n-butyl, 4-(2-trifluoromethylphenyl)indenyl]}- hafnium dichloride; diisopropylamidoboranebis 1- 2-isobutyl, 4-(2-trifluoromethylphenyl)indenyl] } - hafnium dichloride; diisopropylamidoboranebis 2-sec-butyl, 4-(2-trifluoromethylphenyl)indenyl] } - hafnium dichloride; diisopropylamidoboranebis 2-tert-butyl, 4-(2 -trifluoromethy lpheny l)indeny 1] }- hafnium dichloride; diisopropylamidoboranebis 2-phenyl, 4-(2-trifluoromethylphenyl)indenyl] } - hafnium dichloride; diisopropylamidoboranebis 1- 2-n-propyl, 4-(2,3 -dimethy lphenyl)indenyl] } hafnium dichloride; diisopropylamidoboranebis 1- 2-isopropyl, 4-(2,3-dimethylphenyl)indenyl] } hafnium dichloride; diisopropylamidoboranebis 2-n-butyl, 4-(2,3-dimethylphenyl)indenyl] } hafnium dichloride; diisopropylamidoboranebis 2-isobutyl, 4-(2,3-dimethylphenyl)indenyl]} hafnium dichloride; diisopropylamidoboranebis 2-sec-butyl, 4-(2,3-dimethylphenyl)indenyl]} hafnium dichloride; diisopropylamidoboranebis 2-tert-butyl, 4-(2,3-dimethylphenyl)indenyl] } hafnium dichloride; diisopropylamidoboranebis 1- 2-phenyl, 4-(2,3-dimethylphenyl)indenyl] } hafnium dichloride; diisopropylamidoboranebis 2-n-propyl, 4-(2,3,4-trimethylphenyl)indenyl]} hafnium dichloride; diisopropylamidoboranebis 1- 2-isopropyl, 4-(2,3,4-trimethylphenyl)indenyl]} hafnium dichloride; diisopropylamidoboranebis 1- 2-n-butyl, 4-(2,3 ,4-trimethylphenyl)indenyl] } hafnium dichloride; di i sopropy lamidoboranebi s 1- 2-isobutyl, 4-(2,3,4-trimethylphenyl)indenyl]} hafnium dichloride; diisopropylamidoboranebis 1- 2-sec-butyl, 4-(2, 3, 4-trimethy lphenyl)indenyl]} hafnium dichloride; diisopropylamidoboranebis 1- 2-tert-butyl, 4-(2,3, 4-trimethy lpheny l)indenyl] } hafnium dichloride; diisopropylamidoboranebis 1- 2-phenyl, 4-(2,3,4-trimethylphenyl)indenyl]} hafnium dichloride; diisopropylamidoboranebis 1- 2-n-propyl, 4-(2,3,5-trimethylphenyl)indenyl]} hafnium dichloride; diisopropylamidoboranebis 2-isopropyl, 4-(2,3,5-trimethylphenyl)indenyl]} hafnium dichloride; diisopropylamidoboranebis 2-n-butyl, 4-(2,3,5-trimethylphenyl)indenyl]} hafnium dichloride; diisopropylamidoboranebis 2-isobutyl, 4-(2,3,5-trimethy lpheny l)indenyl]} hafnium dichloride; diisopropylamidoboranebis 2-sec-butyl, 4-(2,3,5-trimethylphenyl)indenyl]} hafnium dichloride; diisopropylamidoboranebis 2-tert-butyl, 4-(2,3,5-trimethylphenyl)indenyl]} hafnium dichloride; diisopropylamidoboranebis 2-phenyl, 4-(2,3,5-trimethylphenyl)indenyl]} hafnium dichloride; diisopropylamidoboranebis 2-n-propyl, 4-(2-methylphenyl)indenyl]} hafnium dimethyl; diisopropylamidoboranebis 2-isopropyl, 4-(2-methylphenyl)indenyl]} hafnium dimethyl; diisopropylamidoboranebis 2-n-butyl, 4-(2 -methy lpheny l)indenyl] } hafnium dimethyl; diisopropylamidoboranebis 2-isobutyl, 4-(2-methylphenyl)indenyl]} hafnium dimethyl; diisopropylamidoboranebis 2-sec-butyl, 4-(2-methylphenyl)indenyl]}hafnium dimethyl; diisopropylamidoboranebis 1- 2-tert-butyl, 4-(2-methylphenyl)indenyl]} hafnium dimethyl; diisopropylamidoboranebis 2-phenyl, 4-(2-methylphenyl)indenyl]} hafnium dimethyl; diisopropylamidoboranebis 1- 2-n-propyl, 4-(2-ethylphenyl)indenyl] } hafnium dimethyl; diisopropylamidoboranebis 2-isopropyl, 4-(2-ethylphenyl)indenyl] } hafnium dimethyl; diisopropylamidoboranebis 2-n-butyl, 4-(2-ethylphenyl)indenyl] } hafnium dimethyl; diisopropylamidoboranebis 2-isobutyl, 4-(2-ethylphenyl)indenyl]} hafnium dimethyl; diisopropylamidoboranebis 2-sec-butyl, 4-(2-ethylphenyl)indenyl] } hafnium dimethyl; diisopropylamidoboranebis 2-tert-butyl, 4-(2-ethy lpheny l)indenyl] } hafnium dimethyl; diisopropylamidoboranebis 1- 2-phenyl, 4-(2-ethylphenyl)indenyl] } hafnium dimethyl; diisopropylamidoboranebis 2-n-propyl, 4-(2-n-propylphenyl)indenyl] }hafnium dimethyl; diisopropylamidoboranebis 2-isopropyl, 4-(2-n-propylphenyl)indenyl] } hafnium dimethyl; dii sopropy lamidoboranebi s 2-n-butyl, 4-(2-n-propylphenyl)indenyl] } hafnium dimethyl; diisopropylamidoboranebis 2-isobutyl, 4-(2-n-propylphenyl)indenyl] }hafnium dimethyl; diisopropylamidoboranebis 2-sec-butyl, 4-(2-n-propylphenyl)indenyl] } hafnium dimethyl; diisopropylamidoboranebis 1- 2-tert-butyl, 4-(2-n-propylphenyl)indenyl] } hafnium dimethyl; diisopropylamidoboranebis 1- 2-phenyl, 4-(2 -n-propy lpheny l)indeny 1] } hafnium dimethyl; diisopropylamidoboranebis 1- 2-n-propyl, 4-(2-isopropylphenyl)indenyl] } hafnium dimethyl; diisopropylamidoboranebis 1- 2-isopropyl, 4-(2-isopropylphenyl)indenyl] } hafnium dimethyl; diisopropylamidoboranebis 2-n-butyl, 4-(2-isopropylphenyl)indenyl] }hafnium dimethyl; diisopropylamidoboranebis 2-isobutyl, 4-(2-isopropylphenyl)indenyl] } hafnium dimethyl; diisopropylamidoboranebis 2-sec-butyl, 4-(2-isopropy lpheny l)indenyl] } hafnium dimethyl; diisopropylamidoboranebis 1- 2-tert-butyl, 4-(2-isopropylphenyl)indenyl] } hafnium dimethyl; diisopropylamidoboranebis 1- 2-phenyl, 4-(2-isopropylphenyl)indenyl] }hafnium dimethyl; diisopropylamidoboranebis 2-n-propyl, 4-(2-n-butylphenyl)indenyl] }hafnium dimethyl; diisopropylamidoboranebis 2-isopropyl, 4-(2-n-butylphenyl)indenyl] } hafnium dimethyl; diisopropylamidoboranebis 2-n-butyl, 4-(2-n-butylphenyl)indenyl] } hafnium dimethyl; diisopropylamidoboranebis 2-isobutyl, 4-(2 -n-buty lpheny l)indenyl] } hafnium dimethyl; diisopropylamidoboranebis 1- 2-sec-butyl, 4-(2-n-butylphenyl)indenyl]} hafnium dimethyl; diisopropylamidoboranebis 1- 2-tert-butyl, 4-(2-n-buty lphenyl)indenyl] } hafnium dimethyl; diisopropylamidoboranebis 1- 2-phenyl, 4-(2-n-butylphenyl)indenyl]}hafnium dimethyl; diisopropylamidoboranebis 1- 2-n-propyl, 4-(2-isobutylphenyl)indenyl] } hafnium dimethyl; dii sopropy lamidoboranebi s 1- 2-isopropyl, 4-(2-isobuty lpheny l)indenyl] } hafnium dimethyl; diisopropylamidoboranebis 1- 2-n-butyl, 4-(2-isobutylphenyl)indenyl]}hafnium dimethyl; diisopropylamidoboranebis 2-isobutyl, 4-(2-isobutylphenyl)indenyl] }hafnium dimethyl; diisopropylamidoboranebis 2-sec-butyl, 4-(2-isobutylphenyl)indenyl]} hafnium dimethyl; diisopropylamidoboranebis 2-tert-butyl, 4-(2-isobutylphenyl)indenyl] } hafnium dimethyl; diisopropylamidoboranebis 2-phenyl, 4-(2-isobutylphenyl)indenyl] } hafnium dimethyl; di i sopropy lamidoboranebi s 2-n-propyl, 4-(2-sec-butylphenyl)indenyl] } hafnium dimethyl; diisopropylamidoboranebis 2-isopropyl, 4-(2-sec-butylphenyl)indenyl] } hafnium dimethyl; diisopropylamidoboranebis 1- 2-n-butyl, 4-(2-sec-buty lpheny l)indenyl]} hafnium dimethyl; dii sopropy lamidoboranebi s 2-isobutyl, 4-(2-sec-buty lpheny l)indenyl] } hafnium dimethyl; diisopropylamidoboranebis 1- 2-sec-butyl, 4-(2-sec-butylphenyl)indenyl] } hafnium dimethyl; diisopropylamidoboranebis 1- 2-tert-butyl, 4-(2-sec-butylphenyl)indenyl] } hafnium dimethyl; diisopropylamidoboranebis 1- 2-phenyl, 4-(2-sec-buty lpheny l)indenyl] } hafnium dimethyl; diisopropylamidoboranebis 1- 2-n-propyl, 4-(2 -tert-buty lphenyl)indenyl] } hafnium dimethyl; diisopropylamidoboranebis 1- 2-isopropyl, 4-(2-tert-butylphenyl)indenyl] } hafnium dimethyl; diisopropylamidoboranebis 2-n-butyl, 4-(2 -tert-buty lpheny l)indenyl] } hafnium dimethyl; diisopropylamidoboranebis 2-isobutyl, 4-(2-tert-butylphenyl)indenyl]} hafnium dimethyl; diisopropylamidoboranebis 2-sec-butyl, 4-(2-tert-butylphenyl)indenyl] } hafnium dimethyl; diisopropylamidoboranebis 2-tert-butyl, 4-(2-tert-butylphenyl)indenyl] } hafnium dimethyl; diisopropylamidoboranebis{ 1 -[2-phenyl, 4-(2-tert-butylphenyl)indenyl] }hafnium dimethyl; diisopropylamidoboranebis! 1 -[2-n-propyl, 4-(2-biphenyl)indenyl]}hafnium dimethyl; diisopropylamidoboranebis { 1 - [2-isopropyl, 4-(2-biphenyl)indenyl] } hafnium dimethyl; diisopropylamidoboranebis! 1 -[2-n-butyl, 4-(2-biphenyl)indenyl] }hafnium dimethyl; diisopropylamidoboranebis! 1 -[2-isobutyl, 4-(2-biphenyl)indenyl]} hafnium dimethyl; diisopropylamidoboranebis! 1 -[2-sec-butyl, 4-(2-biphenyl)indenyl]} hafnium dimethyl; diisopropylamidoboranebis { 1 - [2-tert-butyl, 4-(2-biphenyl)indenyl] } hafnium dimethyl; diisopropylamidoboranebis! 1 -[2-phenyl, 4-(2-biphenyl)indenyl]}hafnium dimethyl; diisopropylamidoboranebis! 1 -[2-n-propyl, 4-(2-α-naphthylphenyl)indenyl]} hafnium dimethyl; diisopropylamidoboranebis! 1 -[2-isopropyl, 4-(2-α-naphthylphenyl)indenyl]} hafnium dimethyl; diisopropylamidoboranebis! 1 -[2-n-butyl, 4-(2-α-naphthylphenyl)indenyl] } hafnium dimethyl; diisopropylamidoboranebis! 1 -[2-isobutyl, 4-(2-α-naphthy lpheny l)indenyl]} hafnium dimethyl; diisopropylamidoboranebis! 1 -[2-sec-butyl, 4-(2-α-naphthylphenyl)indenyl]} hafnium dimethyl; diisopropylamidoboranebis! 1 -[2-tert-butyl, 4-(2-α-naphthylphenyl)indenyl]} hafnium dimethyl; diisopropylamidoboranebis! 1 -[2-phenyl, 4-(2-α-naphthylphenyl)indenyl] } hafnium dimethyl; diisopropylamidoboranebis! 1 -[2-n-propyl, 4-(2-β-naphthylphenyl)indenyl]} hafnium dimethyl; diisopropylamidoboranebis 1- 2-isopropyl, 4-(2-β-naphthylphenyl)indenyl]} hafnium dimethyl; diisopropylamidoboranebis 2-n-butyl, 4-(2-β-naphthylphenyl)indenyl] } hafnium dimethyl; diisopropylamidoboranebis 2-isobutyl, 4-(2-β-naphthylphenyl)indenyl] } hafnium dimethyl; diisopropylamidoboranebis 2-sec-butyl, 4-(2-β-naphthylphenyl)indenyl] } hafnium dimethyl; diisopropylamidoboranebis 1- 2-tert-butyl, 4-(2-β-naphthylphenyl)indenyl] } hafnium dimethyl; diisopropylamidoboranebis 1- 2-phenyl, 4-(2-β-naphthylphenyl)indenyl] } hafnium dimethyl; diisopropylamidoboranebis 2-n-propyl, 4-(2-trifluoromethylphenyl)indenyl] } - hafnium dimethyl; diisopropylamidoboranebis 2-isopropyl, 4-(2-trifluoromefhylphenyl)indenyl]}- hafnium dimethyl; diisopropylamidoboranebis 2-n-butyl, 4-(2 -trifluoromethy lphenyl)indenyl]}- hafnium dimethyl; diisopropylamidoboranebis 2-isobutyl, 4-(2-trifluoromethylphenyl)indenyl] } - hafnium dimethyl; diisopropylamidoboranebis 1- 2-sec-butyl, 4-(2-trifluoromethylphenyl)indenyl] } - hafnium dimethyl; diisopropylamidoboranebis 1- 2-tert-butyl, 4-(2 -trifluoromethy lphenyl)indenyl] } - hafnium dimethyl; diisopropylamidoboranebis 2-phenyl, 4-(2 -trifluoromethy lpheny l)indenyl] } - hafnium dimethyl; diisopropylamidoboranebis 2-n-propyl, 4-(2,3-dimethylphenyl)indenyl]} hafnium dimethyl; diisopropylamidoboranebis 2-isopropyl, 4-(2,3-dimethylphenyl)indenyl] } hafnium dimethyl; diisopropylamidoboranebis 2-n-butyl, 4-(2,3-dimethylphenyl)indenyl]} hafnium dimethyl; diisopropylamidoboranebis 1- 2-isobutyl, 4-(2,3-dimethylphenyl)indenyl]} hafnium dimethyl; diisopropylamidoboranebis 1- 2-sec-butyl, 4-(2,3 -dimethy lphenyl)indenyl] } hafnium dimethyl; diisopropylamidoboranebis 1- 2-tert-butyl, 4-(2,3-dimethylphenyl)indenyl] } hafnium dimethyl; diisopropylamidoboranebis 2-phenyl, 4-(2,3 -dimethy lphenyl)indenyl] } hafnium dimethyl; diisopropylamidoboranebis 2-n-propyl, 4-(2,3,4-trimethylphenyl)indenyl]} hafnium dimethyl; diisopropylamidoboranebis 1- 2-isopropyl, 4-(2,3,4-trimethylphenyl)indenyl]} hafnium dimethyl; diisopropylamidoboranebis 1- 2-n-butyl, 4-(2,3,4-trimethylphenyl)indenyl] } hafnium dimethyl; diisopropylamidoboranebis 1- 2-isobutyl, 4-(2,3,4-trimethylphenyl)indenyl]} hafnium dimethyl; dii sopropy lamidoboranebi s 1- 2-sec-butyl, 4-(2,3,4-trimethylphenyl)indenyl]} hafnium dimethyl; diisopropylamidoboranebis 1- 2-tert-butyl, 4-(2,3,4-trimethylphenyl)indenyl]} hafnium dimethyl; diisopropylamidoboranebis 1- 2-phenyl, 4-(2,3,4-trimethylphenyl)indenyl] } hafnium dimethyl; diisopropylamidoboranebis 1- 2-n-propyl, 4-(2,3,5-trimethylphenyl)indenyl]} hafnium dimethyl; diisopropylamidoboranebis 1- 2-isopropyl, 4-(2,3,5-trimethylphenyl)indenyl]} hafnium dimethyl; diisopropylamidoboranebis 1- 2-n-butyl, 4-(2,3,5-trimethylphenyl)indenyl]} hafnium dimethyl; diisopropylamidoboranebis 2-isobutyl, 4-(2,3,5-trimethylphenyl)indenyl]} hafnium dimethyl; diisopropylamidoboranebis 2-sec-butyl, 4-(2,3,5-trimethylphenyl)indenyl]} hafnium dimethyl; diisopropylamidoboranebis 1- 2-tert-butyl, 4-(2,3,5-trimethylphenyl)indenyl]} hafnium dimethyl; diisopropylamidoboranebis 2-phenyl, 4-(2, 3, 5-trimethylphenyl)indenyl]} hafnium dimethyl; diisopropylamidoboranebis 2-n-propyl, 4-(2 -methy lpheny l)indenyl] } zirconium dichloride; diisopropylamidoboranebis 1- 2-isopropyl, 4-(2-methylphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 1- 2-n-butyl, 4-(2-methylphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 2-isobutyl, 4-(2-methylphenyl)indenyl]}zirconium dichloride; diisopropylamidoboranebis 2-sec-butyl, 4-(2-methylphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 2-tert-butyl, 4-(2-methylphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 2-phenyl, 4-(2 -methy lphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 2-n-propyl, 4-(2-ethylphenyl)indenyl]} zirconium dichloride; diisopropylamidoboranebis 2-isopropyl, 4-(2-ethylphenyl)indenyl]} zirconium dichloride; diisopropylamidoboranebis 2-n-butyl, 4-(2-ethylphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 1- 2-isobutyl, 4-(2-ethylphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 1- 2-sec-butyl, 4-(2 -ethy lpheny l)indenyl]} zirconium dichloride; diisopropylamidoboranebis 1- 2-tert-butyl, 4-(2-ethylphenyl)indenyl]}zirconium dichloride; diisopropylamidoboranebis 2-phenyl, 4-(2-ethy lphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 2-n-propyl, 4-(2 -n-propy lphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 2-isopropyl, 4-(2-n-propylphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 2-n-butyl, 4-(2 -n-propy lphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 2-isobutyl, 4-(2 -n-propy lpheny l)indenyl] } zirconium dichloride; diisopropylamidoboranebis 2-sec-butyl, 4-(2-n-propylphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 2-tert-butyl, 4-(2-n-propylphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 2-phenyl, 4-(2 -n-propy lphenyl)indenyl]} zirconium dichloride; diisopropylamidoboranebis 2-n-propyl, 4-(2-isopropylphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 2-isopropyl, 4-(2-isopropylphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 2-n-butyl, 4-(2-isopropylphenyl)indenyl]} zirconium dichloride; diisopropylamidoboranebis 2-isobutyl, 4-(2-isopropylphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 2-sec-butyl, 4-(2-isopropylphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 2-tert-butyl, 4-(2-isopropy lpheny l)indenyl] } zirconium dichloride; diisopropylamidoboranebis 2-phenyl, 4-(2-isopropylphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 2-n-propyl, 4-(2-n-butylphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 2-isopropyl, 4-(2-n-butylphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 2-n-butyl, 4-(2-n-butylphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 2-isobutyl, 4-(2-n-butylphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 2-sec-butyl, 4-(2-n-butylphenyl)indenyl]} zirconium dichloride; diisopropylamidoboranebis 1- 2-tert-butyl, 4-(2-n-butylphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 1- 2-phenyl, 4-(2-n-butylphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 1- 2-n-propyl, 4-(2-isobutylphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 1- 2-isopropyl, 4-(2-isobutylphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 1- 2-n-butyl, 4-(2-isobuty lpheny l)indeny 1] } zirconium dichloride; diisopropylamidoboranebis 1- 2-isobutyl, 4-(2-isobutylphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 1- 2-sec-butyl, 4-(2-isobutylphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 1- 2-tert-butyl, 4-(2-isobutylphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 1- 2-phenyl, 4-(2-isobuty lphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 1- 2-n-propyl, 4-(2-sec-butylphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 1- 2-isopropyl, 4-(2-sec-butylphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 1- 2-n-butyl, 4-(2-sec-butylphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 2-isobutyl, 4-(2-sec-butylphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 2-sec-butyl, 4-(2-sec-butylphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 2-tert-butyl, 4-(2-sec-butylphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 2-phenyl, 4-(2-sec-butylphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 2-n-propyl, 4-(2-tert-butylphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 2-isopropyl, 4-(2-tert-butylphenyl)indenyl]} zirconium dichloride; diisopropylamidoboranebis 2-n-butyl, 4-(2-tert-butylphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 2-isobutyl, 4-(2-tert-butylphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 2-sec-butyl, 4-(2 -tert-buty lphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 2-tert-butyl, 4-(2-tert-butylphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 2-phenyl, 4-(2-tert-butylphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 2-n-propyl, 4-(2-biphenyl)indenyl]} zirconium dichloride; diisopropylamidoboranebis 2-isopropyl, 4-(2-biphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 2-n-butyl, 4-(2-biphenyl)indenyl]} zirconium dichloride; diisopropylamidoboranebis 2-isobutyl, 4-(2-biphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 2-sec-butyl, 4-(2-biphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 2-tert-butyl, 4-(2-biphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 2-pheny 1, 4-(2-bipheny l)indenyl] } zirconium dichloride; diisopropylamidoboranebis 1- 2-n-propyl, 4-(2-α-naphthylphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 1- 2-isopropyl, 4-(2-α-naphthylphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 2-n-butyl, 4-(2-α-naphthylphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 2-isobutyl, 4-(2-α-naphthylphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 1- 2-sec-butyl, 4-(2-α-naphthylphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 1- 2-tert-butyl, 4-(2-α-naphthylpheny l)indeny 1] } zirconium dichloride; diisopropylamidoboranebis 1- 2-phenyl, 4-(2-α-naphthylphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 1- 2-n-propyl, 4-(2-β-naphthylphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 2-isopropyl, 4-(2-β-naphthylphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 2-n-butyl, 4-(2-β-naphthy lpheny l)indenyl] } zirconium dichloride; diisopropylamidoboranebis 2-isobutyl, 4-(2-β-naphthylphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 2-sec-butyl, 4-(2-β-naphthy lpheny l)indenyl] } zirconium dichloride; diisopropylamidoboranebis 2-tert-butyl, 4-(2-β-naphthylphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 2-phenyl, 4-(2-β-naphthy lphenyl)indeny 1] } zirconium dichloride; diisopropylamidoboranebis 1- 2-n-propyl, 4-(2 -trifluoromethy lphenyl)indenyl] } - zirconium dichloride; diisopropylamidoboranebis 2-isopropyl, 4-(2-trifluoromethylphenyl)indenyl] } - zirconium dichloride; diisopropylamidoboranebis 2-n-butyl, 4-(2 -trifluoromethy lphenyl)indenyl] } - zirconium dichloride; diisopropylamidoboranebis 1- 2-isobutyl, 4-(2 -trifluoromethy lphenyl)indenyl] } - zirconium dichloride; diisopropylamidoboranebis 2-sec-butyl, 4-(2-trifluoromethylphenyl)indenyl]}- zirconium dichloride; diisopropylamidoboranebis 2-tert-butyl, 4-(2-trifluoromethylphenyl)indenyl] } - zirconium dichloride; diisopropylamidoboranebis 2-phenyl, 4-(2-trifluoromethylphenyl)indenyl] } - zirconium dichloride; diisopropylamidoboranebis 2-n-propyl, 4-(2,3-dimethylphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 2-isopropyl, 4-(2,3-dimethylphenyl)indenyl]} zirconium dichloride; diisopropylamidoboranebis 1- 2-n-butyl, 4-(2,3-dimethylphenyl)indenyl]} zirconium dichloride; diisopropylamidoboranebis 1- 2-isobutyl, 4-(2,3-dimethylphenyl)indenyl]} zirconium dichloride; diisopropylamidoboranebis 1- 2-sec-butyl, 4-(2,3-dimethylphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 1- 2-tert-butyl, 4-(2,3-dimethylphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 1- 2-phenyl, 4-(2,3-dimethylphenyl)indenyl]} zirconium dichloride; diisopropylamidoboranebis 1- 2-n-propyl, 4-(2,3 ,4-trimethylphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 1- 2-isopropyl, 4-(2,3,4-trimethylphenyl)indenyl]} zirconium dichloride; diisopropylamidoboranebis 2-n-butyl, 4-(2,3,4-trimethylphenyl)indenyl]} zirconium dichloride; diisopropylamidoboranebis 2-isobutyl, 4-(2,3,4-trimethylphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 2-sec-butyl, 4-(2,3, 4-trimethy lphenyl)indenyl]} zirconium dichloride; diisopropylamidoboranebis 2-tert-butyl, 4-(2,3,4-trimethylphenyl)indenyl] } zirconium dichloride; diisopropylamidoboranebis 2-phenyl, 4-(2,3,4-trimethylphenyl)indenyl]} zirconium dichloride; diisopropylamidoboranebis 2-n-propyl, 4-(2,3,5-trimethylphenyl)indenyl]} zirconium dichloride; diisopropylamidoboranebis 2-isopropyl, 4-(2,3,5-trimethylphenyl)indenyl]} zirconium dichloride; diisopropylamidoboranebis 2-n-butyl, 4-(2,3,5-trimethylphenyl)indenyl]} zirconium dichloride; diisopropylamidoboranebis 2-isobutyl, 4-(2,3,5-trimethylphenyl)indenyl]} zirconium dichloride; diisopropylamidoboranebis 2-sec-butyl, 4-(2,3, 5-trimethy lpheny l)indenyl]} zirconium dichloride; diisopropylamidoboranebis 2-tert-butyl, 4-(2,3, 5-trimethy lphenyl)indenyl]} zirconium dichloride; di i sopropy lamidoboranebi s 2-phenyl, 4-(2,3,5-trimethylphenyl)indenyl]} zirconium dichloride; diisopropylamidoboranebis 2-n-propyl, 4-(2-methylphenyl)indenyl]} zirconium dimethyl; diisopropylamidoboranebis 2-isopropyl, 4-(2-methylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 2-n-butyl, 4-(2-methylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 2-isobutyl, 4-(2-methylphenyl)indenyl]} zirconium dimethyl; diisopropylamidoboranebis 2-sec-butyl, 4-(2 -methy lphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis! 2-tert-butyl, 4-(2-methylpheny l)indeny 1] } zirconium dimethyl; diisopropylamidoboranebis { 2-phenyl, 4-(2-methylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis! 2-n-propyl, 4-(2-ethylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis! 2-isopropyl, 4-(2-ethy lphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis! 2-n-butyl, 4-(2-ethylphenyl)indenyl]} zirconium dimethyl; diisopropylamidoboranebis { 2-isobutyl, 4-(2-ethylphenyl)indenyl]} zirconium dimethyl; diisopropylamidoboranebis { 2-sec-butyl, 4-(2-ethylphenyl)indenyl] }zirconium dimethyl; diisopropylamidoboranebis! 2-tert-butyl, 4-(2-ethylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis { 2-phenyl, 4-(2-ethylphenyl)indenyl]} zirconium dimethyl; diisopropylamidoboranebis { 2-n-propyl, 4-(2-n-propylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis { 2-isopropyl, 4-(2-n-propylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis { 2-n-butyl, 4-(2 -n-propy lphenyl)indeny 1] } zirconium dimethyl; diisopropylamidoboranebis { 2-isobutyl, 4-(2 -n-propy lphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis { 2-sec-butyl, 4-(2-n-propylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis { 2-tert-butyl, 4-(2-n-propylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis { 2-phenyl, 4-(2-n-propylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 2-n-propyl, 4-(2-isopropylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 2-isopropyl, 4-(2-isopropylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 2-n-butyl, 4-(2-isopropylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 1- 2-isobutyl, 4-(2-i sopropy lpheny l)indenyl]} zirconium dimethyl; diisopropylamidoboranebis 1- 2-sec-butyl, 4-(2-isopropylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 1- 2-tert-butyl, 4-(2-isopropylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 1- 2-phenyl, 4-(2-isopropylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 2-n-propyl, 4-(2-n-butylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 2-isopropyl, 4-(2-n-butylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 2-n-butyl, 4-(2-n-butylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 1- 2-isobutyl, 4-(2-n-butylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 2-sec-butyl, 4-(2-n-butylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 1- 2-tert-butyl, 4-(2-n-butylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 2-phenyl, 4-(2-n-butylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 2-n-propyl, 4-(2-isobutylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 2-isopropyl, 4-(2-isobutylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 2-n-butyl, 4-(2-isobutylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 2-isobutyl, 4-(2-isobutylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 2-sec-butyl, 4-(2-isobutylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 2-tert-butyl, 4-(2-isobutylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 1- 2-phenyl, 4-(2-isobutylphenyl)indenyl]} zirconium dimethyl; diisopropylamidoboranebis 1- 2-n-propyl, 4-(2-sec-butylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 1- 2-isopropyl, 4-(2-sec-butylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 1- 2-n-butyl, 4-(2-sec-butylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 1- 2-isobutyl, 4-(2-sec-butylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 1- 2-sec-butyl, 4-(2-sec-butylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 1- 2-tert-butyl, 4-(2-sec-butylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 1- 2-phenyl, 4-(2-sec-butylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 1- 2-n-propyl, 4-(2 -tert-buty lphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 2-isopropyl, 4-(2-tert-butylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 2-n-butyl, 4-(2-tert-butylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 1- 2-isobutyl, 4-(2-tert-butylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 1- 2-sec-butyl, 4-(2-tert-butylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 1- 2-tert-butyl, 4-(2-tert-butylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 1- 2-phenyl, 4-(2-tert-butylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 1- 2-n-propyl, 4-(2-biphenyl)indenyl]} zirconium dimethyl; diisopropylamidoboranebis 1- 2-isopropyl, 4-(2-biphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 2-n-butyl, 4-(2-biphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 1- 2-isobutyl, 4-(2-biphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 1- 2-sec-butyl, 4-(2-biphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 1- 2-tert-butyl, 4-(2-biphenyl)indeny 1] } zirconium dimethyl; diisopropylamidoboranebis 1- 2-phenyl, 4-(2-biphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 1- 2-n-propyl, 4-(2-α-naphthylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 2-isopropyl, 4-(2-α-naphthylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 1- 2-n-butyl, 4-(2-α-naphthylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 1- 2-isobutyl, 4-(2-α-naphthylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 1- 2-sec-butyl, 4-(2-α-naphthy lpheny l)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 1- 2-tert-butyl, 4-(2-α-naphthy lpheny l)indenyl]} zirconium dimethyl; diisopropylamidoboranebis 1- 2-phenyl, 4-(2-α-naphthylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 1- 2-n-propyl, 4-(2-β-naphthylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 1- 2-isopropyl, 4-(2-β-naphthylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 2-n-butyl, 4-(2-β-naphthy lpheny l)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 2-isobutyl, 4-(2-β-naphthy lphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 2-sec-butyl, 4-(2-β-naphthylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 2-tert-butyl, 4-(2-β-naphthylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 2-phenyl, 4-(2-β-naphthy lpheny l)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 2-n-propyl, 4-(2-trifluoromethylphenyl)indenyl] } - zirconium dimethyl; diisopropylamidoboranebis 2-isopropyl, 4-(2 -trifluoromethy lphenyl)indenyl]}- zirconium dimethyl; diisopropylamidoboranebis 2-n-butyl, 4-(2-trifluoromethylphenyl)indenyl] } - zirconium dimethyl; diisopropylamidoboranebis 2-isobutyl, 4-(2 -trifluoromethy lphenyl)indenyl] } - zirconium dimethyl; di i sopropy lamidoboranebi s 2-sec-butyl, 4-(2-trifluoromethylphenyl)indenyl] } - zirconium dimethyl; diisopropylamidoboranebis 2-tert-butyl, 4-(2-trifluoromethylphenyl)indenyl] } - zirconium dimethyl; diisopropylamidoboranebis 2-phenyl, 4-(2-trifluoromethylphenyl)indenyl] } - zirconium dimethyl; diisopropylamidoboranebis 1- 2-n-propyl, 4-(2, 3 -dimethy lphenyl)indenyl]} zirconium dimethyl; diisopropylamidoboranebis 2-isopropyl, 4-(2,3-dimethylphenyl)indenyl]} zirconium dimethyl; diisopropylamidoboranebis 2-n-butyl, 4-(2,3-dimethylphenyl)indenyl]} zirconium dimethyl; diisopropylamidoboranebis 2-isobutyl, 4-(2,3-dimethylphenyl)indenyl]} zirconium dimethyl; diisopropylamidoboranebis 2-sec-butyl, 4-(2, 3 -dimethy lpheny l)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 2-tert-butyl, 4-(2,3-dimethylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 2-phenyl, 4-(2,3-dimethylphenyl)indenyl]} zirconium dimethyl; diisopropylamidoboranebis 2-n-propyl, 4-(2,3,4-trimethylphenyl)indenyl]} zirconium dimethyl; diisopropylamidoboranebis 2-isopropyl, 4-(2,3,4-trimethylphenyl)indenyl]} zirconium dimethyl; diisopropylamidoboranebis 2-n-butyl, 4-(2,3,4-trimethylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 2-isobutyl, 4-(2,3,4-trimethylphenyl)indenyl] } zirconium dimethyl; diisopropylamidoboranebis 2-sec-butyl, 4-(2,3,4-trimethylphenyl)indenyl]} zirconium dimethyl; diisopropylamidoboranebis 2-tert-butyl, 4-(2,3,4-trimethylphenyl)indenyl]} zirconium dimethyl; diisopropylamidoboranebis 2-phenyl, 4-(2,3,4-trimethylphenyl)indenyl]} zirconium dimethyl; diisopropylamidoboranebis 2-n-propyl, 4-(2,3,5-trimethylphenyl)indenyl]} zirconium dimethyl; diisopropylamidoboranebis 2-isopropyl, 4-(2,3,5-trimethylphenyl)indenyl]} zirconium dimethyl; diisopropylamidoboranebis 2-n-butyl, 4-(2,3,5-trimethylphenyl)indenyl]} zirconium dimethyl; diisopropylamidoboranebis{ 1 -[2-isobutyl, 4-(2,3,5-trimethylphenyl)indenyl]} zirconium dimethyl; diisopropylamidoboranebis! l-[2-sec-butyl, 4-(2,3,5-trimethylphenyl)indenyl]} zirconium dimethyl; diisopropylamidoboranebis! 1 -[2-tert-butyl, 4-(2,3,5-trimethylphenyl)indenyl]} zirconium dimethyl; diisopropylamidoboranebis! l-[2-phenyl, 4-(2,3,5-trimethylphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 1- 2 -n-propyl, 4-(2-methylphenyl)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 1- 2-isopropyl, 4-(2-methylphenyl)indenyl]} zirconium dichloride; bis(trimethylsilyl)amidoboranebis 1- 2-n-butyl, 4-(2 -methy lphenyl)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 1- 2-isobutyl, 4-(2-methylphenyl)indenyl] } zirconium dichloride; bis(trimefhylsilyl)amidoboranebis 1- 2-sec-butyl, 4-(2-methylphenyl)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 1- 2-tert-butyl, 4-(2 -methy lpheny l)indenyl]} zirconium dichloride; bis(trimethylsilyl)amidoboranebis 1- 2-phenyl, 4-(2-methylphenyl)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 1- 2-n-propyl, 4-(2-ethylphenyl)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 1- 2-isopropyl, 4-(2-ethylphenyl)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 1- 2-n-butyl, 4-(2-ethylphenyl)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 1- 2-isobutyl, 4-(2-ethylphenyl)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 1- 2-sec-butyl, 4-(2-ethylphenyl)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-tert-butyl, 4-(2-ethylphenyl)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-phenyl, 4-(2-ethylphenyl)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-n-propyl, 4-(2-n-propylphenyl)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-isopropyl, 4-(2-n-propylphenyl)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-n-butyl, 4-(2-n-propylphenyl)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-isobutyl, 4-(2-n-propylphenyl)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-sec-butyl, 4-(2-n-propylphenyl)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-tert-butyl, 4-(2-n-propylphenyl)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-phenyl, 4-(2 -n-propy lpheny l)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-n-propyl, 4-(2-isopropylphenyl)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-isopropyl, 4-(2-isopropylphenyl)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-n-butyl, 4-(2-isopropylphenyl)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-isobutyl, 4-(2-isopropylphenyl)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-sec-butyl, 4-(2-isopropylphenyl)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-tert-butyl, 4-(2-isopropylphenyl)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-phenyl, 4-(2-isopropylphenyl)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-n-propyl, 4-(2-n-butylphenyl)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 1- 2-isopropyl, 4-(2-n-buty lpheny l)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-n-butyl, 4-(2-n-butylphenyl)indenyl]} zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-isobutyl, 4-(2-n-butylphenyl)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 1- 2-sec-butyl, 4-(2-n-butylphenyl)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-tert-butyl, 4-(2-n-butylphenyl)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 1- 2-phenyl, 4-(2-n-butylphenyl)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 1- 2-n-propyl, 4-(2-isobutylphenyl)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 1- 2-isopropyl, 4-(2-isobutylphenyl)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 1- 2-n-butyl, 4-(2-isobuty lpheny l)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 1- 2-isobutyl, 4-(2-isobutylphenyl)indenyl]} zirconium dichloride; bis(trimethylsilyl)amidoboranebis 1- 2-sec-butyl, 4-(2-isobutylphenyl)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-tert-butyl, 4-(2-isobutylphenyl)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-phenyl, 4-(2-isobutylphenyl)indenyl]} zirconium dichloride; bis(trimefhylsilyl)amidoboranebis 1- 2-n-propyl, 4-(2-sec-butylphenyl)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 1- 2-isopropyl, 4-(2-sec-buty lpheny l)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-n-butyl, 4-(2-sec-butylphenyl)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-isobutyl, 4-(2-sec-butylphenyl)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-sec-butyl, 4-(2-sec-butylphenyl)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-tert-butyl, 4-(2-sec-butylphenyl)indenyl]} zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-phenyl, 4-(2-sec-butylphenyl)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-n-propyl, 4-(2-tert-butylphenyl)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-isopropyl, 4-(2-tert-butylphenyl)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-n-butyl, 4-(2-tert-butylphenyl)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-isobutyl, 4-(2-tert-butylphenyl)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-sec-butyl, 4-(2-tert-butylphenyl)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-tert-butyl, 4-(2-tert-butylphenyl)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-phenyl, 4-(2-tert-butylphenyl)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-n-propyl, 4-(2-biphenyl)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-isopropyl, 4-(2-biphenyl)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 1- 2-n-butyl, 4-(2-biphenyl)indenyl]} zirconium dichloride; bis(trimethylsilyl)amidoboranebis 1- 2-isobutyl, 4-(2- bipheny l)indenyl] } zirconium dich oride; bis(trimethylsilyl)amidoboranebis 2-sec-butyl, 4-(2-biphenyl)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-tert-butyl, 4-(2-biphenyl)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 1- 2-phenyl, 4-(2-biphenyl)indenyl] } zirconium dichloride; bis(trimethylsilyl)amidoboranebis 1- 2-n-propyl, 4-(2-α-naphfhylphenyl)- indenyl]} zirconium dichloride; bis(trimethylsilyl)amidoboranebis 1- 2-isopropyl, 4-(2-α-naphthylphenyl)- indenyl]} zirconium dichloride; bis(trimethylsilyl)amidoboranebis 1- 2-n-butyl, 4-(2-α-naphthylphenyl)- indenyl]} zirconium dichloride; bis(trimethylsilyl)amidoboranebis 1- 2-isobutyl, 4-(2-α-naphthylphenyl)- indenyl]} zirconium dichloride; bis(trimethylsilyl)amidoboranebis 1- 2-sec-butyl, 4-(2-α-naphthylphenyl)- indenyl]} zirconium dichloride; bis(trimethylsilyl)amidoboranebis 1- 2 -tert-butyl, 4-(2-α-naphthylphenyl)- indenyl]} zirconium dichloride; bis(trimethylsilyl)amidoboranebis 1- 2 -phenyl, 4-(2-α-naphthylphenyl)- indenyl]} zirconium dichloride; bis(trimethylsilyl)amidoboranebis 1- 2-n-propyl, 4-(2-β-naphthylphenyl)- indenyl]} zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-isopropyl, 4-(2-β-naphthylphenyl)- indenyl]} zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-n-butyl, 4-(2-β-naphthylphenyl)- indenyl]} zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-isobutyl, 4-(2-β-naphthylphenyl)- indenyl]} zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-sec-butyl, 4-(2-β-naphthylphenyl)- indenyl]} zirconium dichloride; bis(trimethylsilyl)amidoboranebis 1- 2-tert-butyl, 4-(2-β-naphthylphenyl)- indenyl]} zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-phenyl, 4-(2-β-naphthylphenyl)- indenyl]} zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-n-propyl, 4-(2-trifluoromethylphenyl)- indenyl]} zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-isopropyl, 4-(2-trifluoromethylphenyl)- indenyl]} zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-n-butyl, 4-(2-trifluoromethylphenyl)- indenyl]} zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-isobutyl, 4-(2-trifluoromethylphenyl)- indenyl]} zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-sec-butyl, 4-(2-trifluoromethylphenyl)- indenyl]} zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-tert-butyl, 4-(2-trifluoromethylphenyl)- indenyl]} zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-phenyl, 4-(2-trifluoromethylphenyl)- indenyl]} zirconium dichloride; bis(trimefhylsilyl)amidoboranebis 2 -n-propyl, 4-(2,3-dimethylphenyl)- indenyl]} zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-isopropyl, 4-(2,3 -dimethy lphenyl)- indenyl]} zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-n-butyl, 4-(2,3-dimethylphenyl)- indenyl]} zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-isobutyl, 4-(2,3-dimethylphenyl)- indenyl]} zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-sec-butyl, 4-(2,3-dimethylphenyl)- indenyl]} zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-tert-butyl, 4-(2,3-dimethylphenyl)- indenyl]} zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-phenyl, 4-(2,3-dimethylphenyl)- indenyl]} zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-n-propyl, 4-(2,3,4-trimethylphenyl)- indenyl]} zirconium dichloride; bis(trimethylsilyl)amidoboranebis 1- 2-isopropyl, 4-(2,3,4-trimethylphenyl)- indenyl]} zirconium dichloride; bis(trimethylsilyl)amidoboranebis 1- 2-n-butyl, 4-(2,3,4-trimethylphenyl)- indenyl]} zirconium dichloride; bis(trimethylsilyl)amidoboranebis 1- 2-isobutyl, 4-(2,3,4-trimethylphenyl)- indenyl]} zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-sec-butyl, 4-(2,3, 4-trimethy lphenyl)- indenyl]} zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-tert-butyl, 4-(2,3, 4-trimethy lphenyl)- indenyl]} zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-phenyl, 4-(2,3 ,4-trimethylphenyl)- indenyl]} zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-n-propyl, 4-(2,3,5-trimethylphenyl)- indenyl]} zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-isopropyl, 4-(2,3, 5 -trimethy lpheny 1)- indenyl]} zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-n-butyl, 4-(2,3,5-trimethylphenyl)- indenyl]} zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-isobutyl, 4-(2,3,5-trimethylphenyl)- indenyl]} zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-sec-butyl, 4-(2,3, 5-trimethy lphenyl)- indenyl]} zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-tert-butyl, 4-(2,3,5-trimethylphenyl)- indenyl]} zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-phenyl, 4-(2,3,5-trimethylphenyl)- indenyl]} zirconium dichloride; bis(trimethylsilyl)amidoboranebis 2-n-propyl, 4-(2-methylphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 2-isopropyl, 4-(2-methylphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 2-n-butyl, 4-(2-methylphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 1- 2-isobutyl, 4-(2 -methy lphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 2-sec-butyl, 4-(2-methylphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 1- 2-tert-butyl, 4-(2-methylphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 1- 2-phenyl, 4-(2 -methy lphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 1- 2-n-propyl, 4-(2-ethylphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 1- 2-isopropyl, 4-(2-ethylphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 2-n-butyl, 4-(2-ethylphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 2-isobutyl, 4-(2-ethylphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 1- 2-sec-butyl, 4-(2-ethylphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 1- 2-tert-butyl, 4-(2-ethylphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 1- 2-phenyl, 4-(2-ethylphenyl)indenyl] } zirconium dimethyl; bis(trimefhylsilyl)amidoboranebis 1- 2-n-propyl, 4-(2-n-propylphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 2-isopropyl, 4-(2-n-propylphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 2-n-butyl, 4-(2-n-propylphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 2-isobutyl, 4-(2-n-propylphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 2-sec-butyl, 4-(2-n-propylphenyl)indenyl] } zirconium dimethyl; bis(trimefhylsilyl)amidoboranebis 2-tert-butyl, 4-(2-n-propylphenyl)indenyl]} zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 1- 2-phenyl, 4-(2-n-propylphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 1- 2-n-propyl, 4-(2-isopropylphenyl)indenyl]} zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 1- 2-isopropyl, 4-(2-isopropylphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 1- 2-n-butyl, 4-(2-isopropylphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 2-isobutyl, 4-(2-isopropylphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 1- 2-sec-butyl, 4-(2-isopropylphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 1- 2-tert-butyl, 4-(2-isopropylphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 1- 2-phenyl, 4-(2-isopropylphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 2-n-propyl, 4-(2 -n-buty lpheny l)indeny 1] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 2-isopropyl, 4-(2-n-butylphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 2-n-butyl, 4-(2-n-butylphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 1- 2-isobutyl, 4-(2-n-butylphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 1- 2-sec-butyl, 4-(2 -n-buty lpheny l)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 1- 2-tert-butyl, 4-(2-n-buty lpheny l)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 1- 2-phenyl, 4-(2-n-butylphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 1- 2-n-propyl, 4-(2-isobutylphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 1- 2-isopropyl, 4-(2-isobutylphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 1- 2-n-butyl, 4-(2-isobutylphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 2-isobutyl, 4-(2-isobutylphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 2-sec-butyl, 4-(2-isobutylphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 2-tert-butyl, 4-(2-isobutylphenyl)indenyl]} zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 2-phenyl, 4-(2-isobutylphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 2-n-propyl, 4-(2-sec-butylphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 2-isopropyl, 4-(2-sec-butylphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 2-n-butyl, 4-(2-sec-butylphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 2-isobutyl, 4-(2-sec-butylphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 2-sec-butyl, 4-(2-sec-butylphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 2-tert-butyl, 4-(2-sec-butylphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 2-phenyl, 4-(2-sec-butylphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 2-n-propyl, 4-(2-tert-butylphenyl)indenyl] } zirconium dimethyl; bi s(trimethy 1 si ly l)amidoboranebi s 1- 2-isopropyl, 4-(2-tert-butylphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 1- 2-n-butyl, 4-(2-tert-butylphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 2-isobutyl, 4-(2-tert-butylphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 2-sec-butyl, 4-(2-tert-butylphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 1- 2-tert-butyl, 4-(2 -tert-buty lpheny l)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 1- 2-phenyl, 4-(2-tert-butylphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 2-n-propyl, 4-(2-biphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 2-isopropyl, 4-(2-biphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 2-n-butyl, 4-(2-biphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 1- 2-isobutyl, 4-(2-biphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 1- 2-sec-butyl, 4-(2-biphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 1- 2-tert-butyl, 4-(2-biphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 2-phenyl, 4-(2-biphenyl)indenyl]} zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 2-n-propyl, 4-(2-α-naphthylphenyl)- indenyl]} zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 2-isopropyl, 4-(2-α-naphthylphenyl)- indenyl]} zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 2-n-butyl, 4-(2-α-naphthylphenyl)- indenyl]} zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 1- 2-isobutyl, 4-(2-α-naphthylphenyl)- indenyl]} zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 2-sec-butyl, 4-(2-α-naphthylphenyl)- indenyl]} zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 2-tert-butyl, 4-(2-α-naphthylphenyl)- indenyl]} zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 2-phenyl, 4-(2-α-naphthylphenyl)- indenyl]} zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 1- 2-n-propyl, 4-(2-β-naphthylphenyl)- indenyl]} zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 1- 2-isopropyl, 4-(2-β-naphthylphenyl)- indenyl]} zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 1- 2-n-butyl, 4-(2-β-naphthylphenyl)- indenyl]} zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 2-isobutyl, 4-(2-β-naphthylphenyl)- indenyl]} zirconium dimethyl; bis(trimethy lsilyl)amidoboranebis 2-sec-butyl, 4-(2-β-naphthylphenyl)- indenyl]} zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 2-tert-butyl, 4-(2-β-naphthylphenyl)- indenyl]} zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 2-phenyl, 4-(2-β-naphthylphenyl)- indenyl]} zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 2-n-propyl, 4-(2-trifluoromethylphenyl)- indenyl]} zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 2-isopropyl, 4-(2-trifluoromethylphenyl)- indenyl]} zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 2-n-butyl, 4-(2-trifluoromethylphenyl)- indenyl]} zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 2-isobutyl, 4-(2-trifluoromethylphenyl)- indenyl]} zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 2-sec-butyl, 4-(2-trifluoromethylphenyl)- indenyl]} zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 1- 2-tert-butyl, 4-(2-trifluoromethylphenyl)- indenyl]} zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 2-phenyl, 4-(2-trifluoromethylphenyl)- . indenyl]} zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 1- 2-n-propyl, 4-(2,3-dimethylphenyl)- indenyl]} zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 2-isopropyl, 4-(2,3-dimethylphenyl)- indenyl]} zirconium dimethyl; bis(trimefhylsilyl)amidoboranebis 1- 2-n-butyl, 4-(2,3-dimethylphenyl)indenyl] } zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 1- 2-isobutyl, 4-(2,3-dimethylphenyl)indenyl]} zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 1- 2-sec-butyl, 4-(2,3-dimethylphenyl)- indenyl]} zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 1- 2-tert-butyl, 4-(2,3-dimethylphenyl)- indenyl]} zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 1- 2-phenyl, 4-(2,3-dimethylphenyl)- indenyl]} zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 1- 2-n-propyl, 4-(2,3,4-trimethylphenyl)- indenyl]} zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 1- 2-isopropyl, 4-(2,3,4-trimethylphenyl)- indenyl]} zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 1- 2-n-butyl, 4-(2,3, 4-trimethy lphenyl)- indenyl]} zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 2-isobutyl, 4-(2,3,4-trimethylphenyl)- indenyl]} zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 1- 2-sec-butyl, 4-(2,3,4-trimethylphenyl)- indenyl]} zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 2-tert-butyl, 4-(2,3,4-trimethylphenyl)- indenyl]} zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 1- 2-phenyl, 4-(2,3,4-trimethylphenyl)- indenyl]} zirconium dimethyl; bis(trimethylsilyl)amidoboranebis 2-n-propyl, 4-(2,3,5-trimethylphenyl)- indenyl]} zirconium dimethyl; bis(trimethylsilyl)amidoboranebis{ 1 -[2-isopropyl, 4-(2,3,5-trimethylphenyl)- indenyl]} zirconium dimethyl; bis(trimethylsilyl)amidoboranebis{ 1 -[2-n-butyl, 4-(2,3,5-trime /lphenyl)- indenyl]} zirconium dimethyl; bis(trimethylsilyl)amidoboranebis! 1 -[2-isobutyl, 4-(2,3,5-trimethylphenyl)- indenyl]} zirconium dimethyl; bis(trimethylsilyl)amidoboranebis{ 1 -[2-sec-butyl, 4-(2,3,5-trimethylphenyl)- indenyl]} zirconium dimethyl; bis(trimethylsilyl)amidoboranebis! l-[2-tert-butyl, 4-(2,3,5-trimethylphenyl)- indenyl] } zirconium dimethyl ; bis(trimethylsilyl)amidoboranebis! l-[2 -phenyl, 4-(2,3,5-trimethylphenyl)- indenyl]}zircqnium dimethyl; dimethylsilanediylbis! 1 -[2-n-propyl, 4-(2-methylphenyl)indenyl]} zirconium η4-
1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-isopropyl, 4-(2-methylphenyl)indenyl]} zirconium η4-
1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis! l-[2 -n-butyl, 4-(2-methylphenyl)indenyl]} zirconium η4-
1 ,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis! 1 -[2-isobutyl, 4-(2-methylphenyl)indenyl]} zirconium η4- l,4-diphenyl-l,3-butadiene; dimethylsilanediylbis! 1 -[2-sec-butyl, 4-(2 -methy lphenyl)indenyl]} zirconium η4-
1 ,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis! 1 -[2-tert-butyl, 4-(2-methylphenyl)indenyl]} zirconium η4-
1 ,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis! 1 -[2-phenyl, 4-(2-methylphenyl)indenyl] } zirconium η4-l,4- diphenyl- 1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-n-propyl, 4-(2-ethylphenyl)indenyl]} zirconium η4-l,4- diphenyl-1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-isopropyl, 4-(2-ethylphenyl)indenyl]} zirconium η4- 1 ,4-diphenyl- 1 ,3-butadiene; dimethy lsilanediylbis! 1 -[2-n-butyl, 4-(2-ethy lpheny l)indenyl]} zirconium η4-l,4- diphenyl-l,3-butadiene; dimethylsilanediylbis! 1 -[2-isobutyl, 4-(2-ethylphenyl)indenyl]}zirconium η4-l,4- diphenyl-1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-sec-butyl, 4-(2-ethylphenyl)indenyl]} zirconium η4-
1 ,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis! 1 -[2-tert-butyl, 4-(2-ethylphenyl)indenyl] } zirconium η4-
1,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis { 1 - [2-phenyl, 4-(2-ethylphenyl)indeny 1] } zirconium η4- 1 ,4- diphenyl-l,3-butadiene; dimethylsilanediylbis! 1 -[2-n-propyl, 4-(2-n-propylphenyl)indenyl]} zirconium η4-
1 ,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis! 1 -[2-isopropyl, 4-(2-n-propylphenyl)indenyl] } zirconium η4-l ,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis! 1 -[2-n-butyl, 4-(2-n-propylphenyl)indenyl]} zirconium η4-
1 ,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis! 1 -[2-isobutyl, 4-(2-n-propylphenyl)indenyl]} zirconium η4-
1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-sec-butyl, 4-(2-n-propylphenyl)indenyl]} zirconium η4-l ,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis! 1 -[2-tert-butyl, 4-(2-n-propylphenyl)indenyl] } zirconium η4- 1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-phenyl, 4-(2-n-propylphenyl)indenyl]} zirconium η4-
1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-n-propyl, 4-(2-isopropylphenyl)indenyl]} zirconium η4-l,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis { 1 - [2-isopropyl, 4-(2-isopropy lpheny l)indenyl] } zirconium η4- 1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-n-butyl, 4-(2-isopropylphenyl)indenyl]} zirconium η4- l,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis{ 1 -[2-isobutyl, 4-(2-isopropylphenyl)indenyl]} zirconium η4-
1 ,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis! 1 -[2-sec-butyl, 4-(2-isopropylphenyl)indenyl]} zirconium η4- 1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-tert-butyl, 4-(2-isopropy lpheny l)indenyl]} zirconium η4- 1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-phenyl, 4-(2-isopropylphenyl)indenyl]} zirconium η4- l,4-diphenyl-l,3-butadiene; dimethylsilanediylbis! 1 -[2-n-propyl, 4-(2-n-butylphenyl)indenyl]} zirconium η4- l,4-diphenyl-l,3-butadiene; dimethylsilanediylbis! 1 -[2-isopropyl, 4-(2-n-butylphenyl)indenyl]} zirconium η4-
1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-n-butyl, 4-(2-n-butylphenyl)indenyl]} zirconium η4-
1 ,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis! 1 -[2-isobutyl, 4-(2-n-butylphenyl)indenyl]} zirconium η4-
1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-sec-butyl, 4-(2 -n-buty lpheny l)indenyl]} zirconium η4-
1 ,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis! 1 -[2-tert-butyl, 4-(2-n-butylphenyl)indenyl]} zirconium η4- l,4-diphenyl-l,3-butadiene; dimethylsilanediylbis {1 -[2-phenyl, 4-(2-n-butylphenyl)indenyl]} zirconium η4-
1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis {1 -[2-n-propyl, 4-(2-isobutylphenyl)indenyl]} zirconium η - l,4-diphenyl-l,3-butadiene; dimethylsilanediylbis! 1 -[2-isopropyl, 4-(2-isobutylphenyl)indenyl]} zirconium η4-
1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-n-butyl, 4-(2-isobutylphenyl)indenyl]} zirconium η4-
1 ,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis! 1 -[2-isobutyl, 4-(2-isobutylphenyl)indenyl]} zirconium η4- l,4-diphenyl-l,3-butadiene; dimethylsilanediylbis{ 1 -[2-sec-butyl, 4-(2-isobutylphenyl)indenyl] } zirconium η4-
1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-tert-butyl, 4-(2-isobutylphenyl)indenyl]} zirconium η4-
1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis! l-[2-phenyl, 4-(2-isobutylphenyl)indenyl]} zirconium η4-
1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis { 1 - [2-n-propyl, 4-(2-sec-buty lpheny l)indenyl] } zirconium η4- 1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-isopropyl, 4-(2-sec-butylphenyl)indenyl]} zirconium η 4- 1 ,4-diphenyl - 1 ,3-butadiene ; dimethylsilanediylbis! 1 -[2-n-butyl, 4-(2-sec-butylphenyl)indenyl]} zirconium η4-
1 ,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis! 1 -[2-isobutyl, 4-(2-sec-butylphenyl)indenyl]} zirconium η - l,4-diphenyl-l,3-butadiene; dimethylsilanediylbis! 1 -[2-sec-butyl, 4-(2-sec-butylphenyl)indenyl] }zirconium η4-l,4-diphenyl-l,3-butadiene; dimethylsilanediylbis! 1 -[2-tert-butyl, 4-(2-sec-butylphenyl)indenyl]} zirconium η4-l ,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis! 1 -[2-phenyl, 4-(2-sec-butylphenyl)indenyl]} zirconium η4- l,4-diphenyl-l,3-butadiene; dimethylsilanediylbis! 1 -[2-n-propyl, 4-(2-tert-butylphenyl)indenyl]} zirconium η4-l,4-diphenyl-l,3-butadiene; dimethylsilanediylbis! 1 -[2-isopropyl, 4-(2 -tert-buty lphenyl)indenyl]} zirconium η4-l ,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis! 1 -[2-n-butyl, 4-(2-tert-butylphenyl)indenyl]} zirconium η4-
1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-isobutyl, 4-(2-tert-butylphenyl)indenyl]} zirconium η4-
1 ,4-diphenyl- 1 ,3-butadiene ; dimethylsilanediylbis! 1 -[2-sec-butyl, 4-(2-tert-butylphenyl)indenyl]} zirconium η4- 1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis ! 1 - [2-tert-butyl, 4-(2 -tert-buty lphenyl)indenyl] } zirconium η4-l ,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis! 1 -[2-phenyl, 4-(2-tert-butylphenyl)indenyl]} zirconium η4- l ,4-diphenyl-l,3-butadiene; dimethylsilanediylbis! l-[2 -n-propyl, 4-(2-biphenyl)indenyl]} zirconium η4-l ,4- diphenyl-l ,3-butadiene; dimethylsilanediylbis! 1 -[2-isopropyl, 4-(2-biphenyl)indenyl] } zirconium η4-l ,4- diphenyl- 1 ,3-butadiene; dimethylsilanediylbis ! 1 - [2-n-butyl, 4-(2-bipheny l)indeny 1] } zirconium η4- 1 ,4- diphenyl-l ,3-butadiene; dimethylsilanediylbis { 1 -[2-isobutyl, 4-(2-biphenyl)indenyl] } zirconium η4- 1 ,4- diphenyl-l ,3-butadiene; dimethylsilanediylbis! 1 -[2-sec-butyl, 4-(2 -biphenyl)indenyl]} zirconium η4- 1,4- diphenyl-1 ,3-butadiene; dimethylsilanediylbis { 1 -[2-tert-butyl, 4-(2-biphenyl)indenyl]} zirconium η4-l ,4- diphenyl- 1 ,3-butadiene; dimethylsilanediylbis { 1 - [2-phenyl, 4-(2-biphenyl)indenyl] } zirconium η4- 1 ,4- diphenyl- 1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-n-propyl, 4-(2-α-naphthy lpheny l)indenyl]} zirconium η4- 1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis! l-[2-isopropyl, 4-(2-α-naphthylphenyl)indenyl]}zirconium η4- 1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis! l-[2-n-butyl, 4-(2-α-naphthylphenyl)indenyl]}zirconium η4-l ,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis! 1 -[2-isobutyl, 4-(2-α-naphthy lpheny l)indenyl]} zirconium η4- 1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-sec-butyl, 4-(2-α-naphthylphenyl)indenyl]} zirconium η4- 1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis! l-[2 -tert-butyl, 4-(2-α-naphthylphenyl)indenyl]}zirconium η4- 1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis{ 1 -[2-phenyl, 4-(2-α-naphthy lpheny l)indenyl]} zirconium η4-
1 ,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis! 1 -[2-n-propyl, 4-(2-β-naphthylphenyl)indenyl]} zirconium η 4- 1 ,4-diphenyl - 1 ,3-butadiene ; dimethylsilanediylbis! 1 -[2-isopropyl, 4-(2-β-naphthylphenyl)indenyl]} zirconium η4- 1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-n-butyl, 4-(2-β-naphthylphenyl)indenyl]} zirconium η4- 1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-isobutyl, 4-(2-β-naphthy lpheny l)indeny 1] } zirconium η4-l ,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis! 1 -[2-sec-butyl, 4-(2-β-naphthylphenyl)indenyl]} zirconium η4- 1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-tert-butyl, 4-(2-β-naphthylphenyl)indenyl]} zirconium η4-l,4-diphenyl-l,3-butadiene; dimethylsilanediylbis! 1 -[2-phenyl, 4-(2-β-naphthylphenyl)indenyl]} zirconium η4-
1 ,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis! 1 -[2-n-propyl, 4-(2-trifluoromethylphenyl)indenyl] } zirconium η4-l ,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis! 1 -[2-isopropyl, 4-(2-trifluoromethylphenyl)indenyl] } zirconium η4- 1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-n-butyl, 4-(2-trifluoromethylphenyl)indenyl]} zirconium η4-l,4-diphenyl-l,3-butadiene; dimethylsilanediylbis! 1 -[2-isobutyl, 4-(2 -trifluoromethy lphenyl)indenyl] } zirconium η4-l ,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis! l-[2-sec -butyl, 4-(2-trifluoromethylphenyl)indenyl]} zirconium η4-l,4-diphenyl-l,3-butadiene; dimethylsilanediylbis! 1 -[2-tert-butyl, 4-(2-trifluoromethylphenyl)indenyl]} zirconium η4-l,4-diphenyl-l,3-butadiene; dimethylsilanediylbis ! 1 - [2-phenyl, 4-(2-trifluoromethylphenyl)indeny 1] } zirconium η4-l,4-diphenyl-l,3-butadiene; dimethylsilanediylbis{ 1 -[2-n-propyl, 4-(2,3-dimethylphenyl)indenyl] }zirconium η4- 1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-isopropyl, 4-(2,3-dimethylphenyl)indenyl]}zirconium η4-l ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-n-butyl, 4-(2,3-dimethylphenyl)indenyl]} zirconium η4-l,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis! 1 -[2-isobutyl, 4-(2,3-dimethylphenyl)indenyl]}zirconium η4-l,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis! 1 -[2-sec-butyl, 4-(2,3 -dimethy lpheny l)indenyl]} zirconium η4- 1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis { 1 - [2-tert-butyl, 4-(2,3 -dimethy lphenyl)indenyl] } zirconium η4-l,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis! 1 -[2-phenyl, 4-(2,3-dimethylphenyl)indenyl]}zirconium η4-
1 ,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis { 1 -[2-n-propyl, 4-(2,3,4-trimethylphenyl)indenyl]}zirconium η4- 1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-isopropyl, 4-(2,3,4-trimethylphenyl)indenyl]} zirconium η4-l ,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis! 1 -[2-n-butyl, 4-(2,3,4-trimethylphenyl)indenyl]}zirconium η4-l,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis! 1 -[2-isobutyl, 4-(2,3,4-trimethylphenyl)indenyl]} zirconium η4- 1 ,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis! 1 -[2-sec-butyl, 4-(2,3,4-trimethylphenyl)indenyl]} zirconium η4-l,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis! l-[2 -tert-butyl, 4-(2,3, 4-trimethy lpheny l)indenyl]} zirconium η4-l,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis! 1 -[2 -phenyl, 4-(2,3,4-trimethylphenyl)indenyl]} zirconium η4-l ,4-diphenyl-l,3-butadiene; dimethylsilanediylbis { 1 -[2-n-propyl, 4-(2,3,5-trimethylphenyl)indenyl]}zirconium η4-l,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis{ l -[2-isopropyl, 4-(2,3,5-trimethylphenyl)indenyl]} zirconium η4-l ,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis! l-[2-n-butyl, 4-(2,3,5-trimethylphenyl)indenyl]}zirconium η4- 1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis { 1 - [2-isobutyl, 4-(2,3 ,5 -trimethylpheny l)indeny 1] } zirconium η4-l ,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis! l-[2-sec -butyl, 4-(2,3,5-trimethylphenyl)indenyl]} zirconium η4-l,4-diphenyl-l,3-butadiene; dimethylsilanediylbis! 1 -[2-tert-butyl, 4-(2,3,5-trimethylphenyl)indenyl]} zirconium η4-l,4-diphenyl-l,3-butadiene; dimethylsilanediylbis! 1 -[2-phenyl, 4-(2,3,5-trimethylphenyl)indenyl]}zirconium η4-l,4-diphenyl-l,3-butadiene; dimethylsilanediylbis ! 1 - [2-n-propyl, 4-(2-methylphenyl)indenyl] } hafnium η4- 1 ,4- diphenyl- 1,3-butadiene; dimethylsilanediylbis!l-[2-isopropyl, 4-(2 -methy lphenyl)indenyl]} hafnium η4-
1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis { 1 - [2-n-butyl, 4-(2-methylphenyl)indenyl] } hafnium η4- 1 ,4- diphenyl- 1 ,3-butadiene; dimethylsilanediylbis { 1 - [2-isobutyl, 4-(2 -methy lpheny l)indenyl] } hafnium η4- 1 ,4- diphenyl-l,3-butadiene; dimethylsilanediylbis! 1 -[2-sec-butyl, 4-(2-methylphenyl)indenyl]} hafnium η4-
1 ,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis! 1 -[2-tert-butyl, 4-(2-methylphenyl)indenyl]} hafnium η4-
1 ,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis {1 -[2-phenyl, 4-(2-methylphenyl)indenyl]} hafnium η4-l,4- diphenyl-1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-n-propyl, 4-(2-ethylphenyl)indenyl]}hafnium η4-l,4- diphenyl-1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-isopropyl, 4-(2-ethy lpheny l)indenyl] } hafnium η4-l ,4- diphenyl-l,3-butadiene; dimethylsilanediylbis! 1 -[2-n-butyl, 4-(2-ethylphenyl)indenyl] } hafnium η4-l,4- diphenyl-1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-isobutyl, 4-(2-ethylphenyl)indenyl]} hafnium η4-l ,4- diphenyl- 1,3-butadiene; dimethylsilanediylbis! 1 -[2-sec-butyl, 4-(2-ethylphenyl)indenyl]} hafnium η4-l,4- diphenyl-1 ,3-butadiene; dimethylsilanediylbis { 1 -[2-tert-butyl, 4-(2-ethy lphenyl)indenyl]} hafnium η4- 1 ,4- diphenyl-1 ,3-butadiene; dimethylsilanediylbis ! 1 - [2-phenyl, 4-(2-ethy lphenyl)indenyl] } hafnium η4- 1 ,4- diphenyl- 1,3-butadiene; dimethylsilanediylbis! 1 -[2-n-propyl, 4-(2-n-propylphenyl)indenyl]} hafnium η4-
1 ,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis! 1 -[2-isopropyl, 4-(2 -n-propy lpheny l)indenyl]} hafnium η4-
1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-n-butyl, 4-(2-n-propylphenyl)indenyl]}hafnium η4-
1 ,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis! 1 -[2-isobutyl, 4-(2-n-propylphenyl)indenyl]} hafnium η4-
1 ,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis! 1 -[2-sec-butyl, 4-(2 -n-propy lphenyl)indenyl] } hafnium η4- 1 ,4-diphenyl- 1,3 -butadiene; dimethylsilanediylbis! 1 -[2-tert-butyl, 4-(2-n-propylphenyl)indenyl]} hafnium η4-
1 ,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis! l-[2 -phenyl, 4-(2-n-propy lpheny l)indenyl]} hafnium η4-l,4- diphenyl-1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-n-propyl, 4-(2-isopropylphenyl)indenyl]}hafnium η4-
1 ,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis! 1 -[2-isopropyl, 4-(2-isopropylphenyl)indenyl]}hafnium η4-
1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-n-butyl, 4-(2-isopropylphenyl)indenyl] } hafnium η4- 1 ,4-diphenyl- 1,3 -butadiene; dimethylsilanediylbis! 1 -[2-isobutyl, 4-(2-isopropylphenyl)indenyl]} hafnium η4-
1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-sec-butyl, 4-(2-isopropylphenyl)indenyl]}hafnium η4-
1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-tert-butyl, 4-(2-isopropylphenyl)indenyl] } hafnium η4-
1 ,4-diphenyl- 1,3-butadiene; dimethylsilanediylbis {1 -[2-phenyl, 4-(2-isopropylphenyl)indenyl] } hafnium η4-
1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-n-propyl, 4-(2-n-butylphenyl)indenyl]}hafnium η4- 1 ,4-diphenyl- 1,3-butadiene; dimethylsilanediylbis! 1 -[2-isopropyl, 4-(2 -n-buty lphenyl)indenyl]} hafnium η4-
1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis { 1 - [2-n-butyl, 4-(2-n-butylphenyl)indeny 1] } hafnium η4- 1 ,4- diphenyl- 1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-isobutyl, 4-(2-n-butylphenyl)indenyl]} hafnium η4-l,4- diphenyl- 1,3-butadiene; dimethylsilanediylbis! 1 -[2-sec-butyl, 4-(2-n-butylphenyl)indenyl]}hafnium η4-
1 ,4-diphenyl- 1,3-butadiene; dimethylsilanediylbis! 1 -[2-tert-butyl, 4-(2-n-buty lpheny l)indenyl]} hafnium η4- 1 ,4-diphenyl- 1,3-butadiene; dimethylsilanediylbis ! 1 - [2-phenyl, 4-(2 -n-buty lpheny l)indenyl] } hafnium η4- 1 ,4- diphenyl-l ,3-butadiene; dimethylsilanediylbis! 1 -[2-n-propyl, 4-(2-isobutylphenyl)indenyl]} hafnium η4-
1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-isopropyl, 4-(2-isobutylphenyl)indenyl]} hafnium η4-
1 ,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis! 1 -[2-n-butyl, 4-(2-isobuty lpheny l)indenyl]} hafnium η4-l,4- diphenyl-1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-isobutyl, 4-(2-isobutylphenyl)indenyl] } hafnium η4- 1 ,4-diphenyl- 1,3-butadiene; dimethylsilanediylbis! 1 -[2-sec-butyl, 4-(2-isobutylphenyl)indenyl]}hafnium η4-
1 ,4-diphenyl- 1,3-butadiene; dimethylsilanediylbis! 1 -[2-tert-butyl, 4-(2-isobutylphenyl)indenyl]} hafnium η4-
1 ,4-diphenyl- 1,3-butadiene; dimethylsilanediylbis! 1 -[2-phenyl, 4-(2-isobutylphenyl)indenyl]} hafnium η4-l ,4- diphenyl- 1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-n-propyl, 4-(2-sec-buty lphenyl)indenyl]} hafnium η4-
1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-isopropyl, 4-(2-sec-butylphenyl)indenyl]} hafnium η4- 1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-n-butyl, 4-(2-sec-butylphenyl)indenyl]} hafnium η4-
1 ,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis! 1 -[2-isobutyl, 4-(2-sec-butylphenyl)indenyl]}hafnium η4-
1,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis! 1 -[2-sec-butyl, 4-(2-sec-butylphenyl)indenyl]} hafnium η4-
1 ,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis! 1 -[2-tert-butyl, 4-(2-sec-butylphenyl)indenyl]} hafnium η4-
1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-phenyl, 4-(2-sec-butylphenyl)indenyl]}hafnium η4- l,4-diphenyl-l,3-butadiene; dimethylsilanediylbis! l-[2 -n-propyl, 4-(2-tert-butylphenyl)indenyl] }hafnium η4-
1 ,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis! 1 -[2-isopropyl, 4-(2-tert-butylphenyl)indenyl] } hafnium η4-
1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-n-butyl, 4-(2-tert-butylphenyl)indenyl]} hafnium η4-
1 ,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis { 1 -[2-isobutyl, 4-(2-tert-butylphenyl)indenyl] } hafnium η4-
1 ,4-diphenyl- 1,3-butadiene; dimethylsilanediylbis! 1 -[2-sec-butyl, 4-(2-tert-butylphenyl)indenyl]}hafnium η4- 1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis{ 1 -[2-tert-butyl, 4-(2-tert-butylphenyl)indenyl] } hafnium η4-
1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis! l-[2 -phenyl, 4-(2-tert-butylphenyl)indenyl]} hafnium η4-
1 ,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis! 1 -[2-n-propyl, 4-(2-biphenyl)indenyl]} hafnium η -l,4- diphenyl-1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-isopropyl, 4-(2-biphenyl)indenyl]} hafnium η4-l, 4- diphenyl- 1,3-butadiene; dimethylsilanediylbis! l-[2-n-butyl, 4-(2-biphenyl)indenyl]} hafnium η4-l ,4- diphenyl-l,3-butadiene; dimethylsilanediylbis! 1 -[2-isobutyl, 4-(2-biphenyl)indenyl]} hafnium η4-l ,4- diphenyl-r,3-butadiene; dimethylsilanediylbis! 1 -[2-sec-butyl, 4-(2 -bipheny l)indenyl]} hafnium η4- 1,4- diphenyl-1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-tert-butyl, 4-(2-biphenyl)indenyl]} hafnium η4-l,4- diphenyl- 1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-phenyl, 4-(2-biphenyl)indenyl]} hafnium η4-l,4- diphenyl-1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-n-propyl, 4-(2-α-naphthylphenyl)indenyl] } hafnium η4- 1,4-dipheny 1-1, 3 -butadiene; dimethylsilanediylbis! 1 -[2-isopropyl, 4-(2-α-naphthy lpheny l)indenyl]} hafnium η4-l ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-n-butyl, 4-(2-α-naphthy lpheny l)indenyl]} hafnium η -
1 ,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis! 1 -[2-isobutyl, 4-(2-α-naphthylphenyl)indenyl]} hafnium η4-
1 ,4-diphenyl- 1,3-butadiene; dimethylsilanediylbis! 1 -[2-sec-butyl, 4-(2-α-naphthylphenyl)indenyl]}hafnium η -l,4-diphenyl-l,3-butadiene; dimethylsilanediylbis! 1 -[2-tert-butyl, 4-(2-α-naphthy lpheny l)indenyl]} hafnium η4-l,4-diphenyl-l,3-butadiene; dimethylsilanediylbis! 1 -[2-phenyl, 4-(2-α-naphthylphenyl)indenyl]} hafnium η4-
1 ,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis! 1 -[2-n-propyl, 4-(2-β-naphthylphenyl)indenyl]}hafnium η4-
1 ,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis! 1 -[2-isopropyl, 4-(2-β-naphthylphenyl)indenyl]}hafnium η4- 1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-n-butyl, 4-(2-β-naphthy lpheny l)indeny 1] } hafnium η4-
1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-isobutyl, 4-(2-β-naphthy lpheny l)indeny 1] } hafnium η4- 1 ,4-diphenyl- 1,3-butadiene; dimethylsilanediylbis! 1 -[2-sec-butyl, 4-(2-β-naphthylphenyl)indenyl]}hafnium η4- 1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-tert-butyl, 4-(2-β-naphthylphenyl)indenyl]} hafnium η 4- 1 ,4-diphenyl -1,3 -butadiene ; dimethylsilanediylbis! 1 -[2-phenyl, 4-(2-β-naphthy lpheny l)indenyl] } hafnium η4-
1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-n-propyl, 4-(2-trifluoromethylphenyl)indenyl]}- hafnium η4- 1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-isopropyl, 4-(2-trifluoromethy lpheny l)indenyl]}- hafnium η4-l,4-diphenyl-l,3-butadiene; dimethylsilanediylbis! 1 -[2-n-butyl, 4-(2-trifluoromethylphenyl)indenyl]} -hafnium η4-l ,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis! 1 -[2-isobutyl, 4-(2-trifluoromethylphenyl)indenyl]}- hafnium η4-l,4-diphenyl-l,3-butadiene; dimethylsilanediylbis! 1 -[2-sec-butyl, 4-(2-trifluoromethylphenyl)indenyl]}- hafnium η4- 1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-tert-butyl, 4-(2-trifluoromethylphenyl)indenyl]}- hafnium η4-l ,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis !1 -[2-phenyl, 4-(2-trifluoromethylphenyl)indenyl]} -hafnium η4-l,4-diphenyl-l,3-butadiene; dimethylsilanediylbis{ 1 -[2-n-propyl, 4-(2,3-dimethylphenyl)indenyl]}hafnium η4-
1 ,4-diphenyl- 1 ,3 -butadiene; dimethylsilanediylbis! 1 -[2-isopropyl, 4-(2,3-dimethylphenyl)indenyl]}hafnium η4- 1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-n-butyl, 4-(2,3-dimethylphenyl)indenyl]}hafnium η4-
1 ,4-diphenyl-l,3-butadiene; dimethylsilanediylbis! 1 -[2-isobutyl, 4-(2,3-dimethylphenyl)indenyl]}hafnium η4-
1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-sec-butyl, 4-(2,3-dimethylphenyl)indenyl]}hafnium η4-l,4-diphenyl-l,3-butadiene; dimethylsilanediylbis { 1 -[2-tert-butyl, 4-(2,3-dimethylphenyl)indenyl]}hafnium η4- 1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis! 1 -[2-phenyl, 4-(2,3-dimethylphenyl)indenyl]}hafnium η4-
1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis { 1 - [2-n-propyl, 4-(2,3 ,4-trimethy lphenyl)indenyl] } hafnium η4- 1 ,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis! 1 -[2-isopropyl, 4-(2,3,4-trimethylphenyl)indenyl]} hafnium η4- 1 ,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis! 1 -[2-n-butyl, 4-(2,3,4-trimethylphenyl)indenyl]}hafnium η4-l ,4-diphenyl-l,3-butadiene; dimethylsilanediylbis! 1 -[2-isobutyl, 4-(2,3,4-trimethylphenyl)indenyl]}hafnium η4- 1 ,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis! 1 -[2-sec-butyl, 4-(2,3,4-trimethylphenyl)indenyl]} hafnium η4-l,4-diphenyl-l,3-butadiene; dimethylsilanediylbis! 1 -[2-tert-butyl, 4-(2,3,4-trimethylphenyl)indenyl]} hafnium η4-l ,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis! 1 -[2-phenyl, 4-(2,3,4-trimethylphenyl)indenyl] }hafnium η4- 1 ,4-diphenyl- 1 ,3-butadiene; dimethylsilanediylbis { 1 -[2-n-propyl, 4-(2,3,5-trimethylphenyl)indenyl]}hafnium η4-l,4-diphenyl-l,3-butadiene; dimethylsilanediylbis! 1 -[2-isopropyl, 4-(2,3,5-trimethylphenyl)indenyl]} hafnium η 4- 1 ,4-diphenyl -1,3 -butadiene ; dimethylsilanediylbis { 1 - [2-n-butyl, 4-(2,3 ,5 -trimethy lpheny l)indeny 1] } hafnium η 4- 1 ,4-diphenyl -1,3 -butadiene ; dimethylsilanediylbis! 1 -[2-isobutyl, 4-(2,3,5-trimethylphenyl)indenyl]}hafnium η4- 1 ,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis! 1 -[2-sec-butyl, 4-(2,3,5-trimethylphenyl)indenyl]} hafnium η4-l ,4-diphenyl-l ,3-butadiene; dimethylsilanediylbis {1 -[2-tert-butyl, 4-(2,3,5-trimethylphenyl)indenyl]} hafnium η4-l,4-diphenyl-l,3-butadiene; dimethylsilanediylbis !1 -[2-phenyl, 4-(2,3,5-trimethylphenyl)indenyl]}hafnium η4-l,4-diphenyl-l ,3-butadiene;
9-silafluorenediylbis{ l -[2-n-propyl, 4-(2-methylphenyl)indenyl]} zirconium η -
1 ,4-diphenyl- 1 ,3-butadiene; 9-silafluorenediylbis{l -[2-isopropyl, 4-(2-methylphenyl)indenyl]} zirconium η4-
1 ,4-diphenyl- 1,3-butadiene;
9-silafluorenediylbis{ l -[2-n-butyl, 4-(2-methylphenyl)indenyl]} zirconium η4-l,4- diphenyl- 1 ,3-butadiene;
9-silafluorenediylbis{ 1 -[2-isobutyl, 4-(2-methylphenyl)indenyl]} zirconium η4- 1,4-dipheny 1-1, 3 -butadiene;
9-silafluorenediylbis{ 1 -[2-sec-butyl, 4-(2-methylphenyl)indenyl]} zirconium η4-
1 ,4-diphenyl-l ,3-butadiene;
9-silafluorenediylbis{ 1 -[2-tert-butyl, 4-(2-methylphenyl)indenyl]} zirconium η4-
1 ,4-diphenyl-l ,3-butadiene; 9-silafluorenediylbis! 1 -[2-phenyl, 4-(2-methylphenyl)indenyl] } zirconium η4-l,4- diphenyl- 1 ,3-butadiene;
9-silafluorenediylbis { 1 -[2-n-propyl, 4-(2-ethylphenyl)indenyl]} zirconium η4-l,4- diphenyl-1 ,3-butadiene;
9-silafluorenediylbis! 1 -[2-isopropyl, 4-(2-ethylphenyl)indenyl] } zirconium η4-l ,4- diphenyl- 1,3-butadiene; 9-silafluorenediylbis { 1 -[2-n-butyl, 4-(2-ethylphenyl)indenyl]} zirconium η4-l ,4- diphenyl-l ,3-butadiene;
9-silafluorenediylbis { 1 -[2-isobutyl, 4-(2-ethylphenyl)indenyl]} zirconium η4-l,4- diphenyl- 1 ,3-butadiene; 9-silafluorenediylbis { 1 -[2-sec-butyl, 4-(2-ethylphenyl)indenyl]} zirconium η4-l,4- diphenyl- 1 ,3-butadiene;
9-silafluorenediylbis { 1 -[2-tert-butyl, 4-(2-ethylphenyl)indenyl]} zirconium η4-l,4- diphenyl- 1 ,3-butadiene;
9-silafluorenediylbis! 1 -[2-phenyl, 4-(2-ethylphenyl)indenyl]} zirconium η4-l ,4- diphenyl- 1,3-butadiene;
9-silafluorenediylbis! 1 -[2-n-propyl, 4-(2-n-propylphenyl)indenyl]} zirconium η4-
1 ,4-diphenyl- 1 ,3-butadiene;
9-silafluorenediylbis! 1 -[2-isopropyl, 4-(2-n-propy lpheny l)indenyl]} zirconium η4-
1 ,4-diphenyl-l ,3-butadiene; 9-silafluorenediylbis{ l -[2-n-butyl, 4-(2 -n-propy lphenyl)indenyl]} zirconium η4-
1 ,4-diphenyl-l ,3-butadiene;
9-silafluorenediylbis { 1 -[2-isobutyl, 4-(2-n-propy lpheny l)indenyl]} zirconium η4-
1 ,4-diphenyl-l ,3-butadiene;
9-silafluorenediylbis { 1 -[2-sec-butyl, 4-(2-n-propylphenyl)indenyl] } zirconium η4- l,4-diphenyl-l ,3-butadiene;
9-silafluorenediylbis { 1 -[2-tert-butyl, 4-(2-n-propylphenyl)indenyl]} zirconium η4-
1 ,4-diphenyl-l ,3-butadiene;
9-silafluorenediylbis { l-[2-phenyl, 4-(2-n-propylphenyl)indenyl]} zirconium η4-
1 ,4-diphenyl-l ,3-butadiene; 9-silafluorenediylbis{ l -[2-n-propyl, 4-(2-isopropylphenyl)indenyl]} zirconium η4-
1 ,4-diphenyl- 1 ,3-butadiene;
9-silafluorenediylbis{ l-[2-isopropyl, 4-(2-isopropylphenyl)indenyl] } zirconium η4- 1 ,4-diphenyl- 1 ,3-butadiene;
9-silafluorenediylbis { 1 -[2-n-butyl, 4-(2-isopropylphenyl)indenyl]} zirconium η4- 1 ,4-diphenyl- 1 ,3-butadiene; 9-silafluorenediylbis{ 1 -[2-isobutyl, 4-(2-isopropylphenyl)indenyl]} zirconium η4-
1 ,4-diphenyl- 1,3-butadiene;
9-silafluorenediylbis{l-[2-sec -butyl, 4-(2-isopropylphenyl)indenyl]} zirconium η4-l,4-diphenyl-l,3-butadiene; 9-silafluorenediylbis {1 -[2-tert-butyl, 4-(2-isopropylphenyl)indenyl]} zirconium η4- 1 ,4-diphenyl- 1 ,3-butadiene;
9-silafluorenediylbis{l -[2-phenyl, 4-(2-isopropylphenyl)indenyl] } zirconium η4-
1 ,4-diphenyl- 1 ,3-butadiene;
9-silafluorenediylbis { 1 -[2-n-propyl, 4-(2-n-butylphenyl)indenyl]} zirconium η4- 1 ,4-diphenyl- 1,3-butadiene;
9-silafluorenediylbis { 1 -[2-isopropyl, 4-(2-n-butylphenyl)indenyl]} zirconium η4-
1 ,4-diphenyl- 1 ,3-butadiene;
9-silafluorenediylbis! 1 -[2-n-butyl, 4-(2-n-butylphenyl)indenyl] } zirconium η -1,4- diphenyl- 1 ,3-butadiene; 9-silafluorenediylbis { 1 -[2-isobutyl, 4-(2-n-butylphenyl)indenyl]} zirconium η4-
1 ,4-diphenyl- 1,3-butadiene;
9-silafluorenediylbis { 1 -[2-sec-butyl, 4-(2 -n-buty lphenyl)indenyl]} zirconium η -
1 ,4-diphenyl-l ,3-butadiene;
9-silafluorenediylbis { 1 -[2-tert-butyl, 4-(2 -n-buty lphenyl)indenyl] } zirconium η4- 1 ,4-diphenyl- 1,3-butadiene;
9-silafluorenediylbis { 1 -[2-phenyl, 4-(2-n-butylphenyl)indenyl] } zirconium η4- 1 ,4- diphenyl-l, 3-butadiene;
9-silafluorenediylbis { 1 -[2-n-propyl, 4-(2-isobutylphenyl)indenyl]} zirconium η4-
1 ,4-diphenyl- 1 ,3-butadiene; 9-silafluorenediylbis { 1 -[2-isopropyl, 4-(2-isobutylphenyl)indenyl]} zirconium η4-
1 ,4-diphenyl- 1 ,3-butadiene;
9-silafluorenediylbis {1 -[2-n-butyl, 4-(2-isobutylphenyl)indenyl]} zirconium η4-
1 ,4-diphenyl- 1,3-butadiene;
9-silafluorenediylbis! 1 -[2-isobutyl, 4-(2-isobuty lpheny l)indenyl]} zirconium η4- 1 ,4-diphenyl- 1,3-butadiene; 9-s lafluorenediylbis! 1 -[2-sec-butyl, 4-(2-isobutylphenyl)indenyl]} zirconium η4- 1,4 •diphenyl- 1,3-butadiene; 9-s lafluorenediylbis! 1 -[2-tert-butyl, 4-(2-isobutylphenyl)indenyl]}zirconium η4-
1,4 diphenyl- 1 ,3-butadiene; 9-s lafluorenediylbis! 1 -[2-phenyl, 4-(2-isobutylphenyl)indenyl]} zirconium η4-
1,4 diphenyl-1 ,3-butadiene; 9-s lafluorenediylbis! 1 -[2-n-propyl, 4-(2-sec-butylphenyl)indenyl]} zirconium η4-
1,4 ■diphenyl-1 ,3-butadiene; 9-s lafluorenediylbis! 1 -[2-isopropyl, 4-(2-sec-butylphenyl)indenyl] } zirconium η4- 1 ,4-diphenyl-l ,3-butadiene; 9-s lafluorenediylbis! 1 -[2-n-butyl, 4-(2-sec-butylphenyl)indenyl]} zirconium η4-
1,4 ■diphenyl-1 ,3-butadiene; 9-s lafluorenediylbis! 1 -[2-isobutyl, 4-(2-sec-butylphenyl)indenyl]} zirconium η4-
1,4 diphenyl-1 ,3-butadiene; 9-s lafluorenediylbis! 1 -[2-sec-butyl, 4-(2-sec-butylphenyl)indenyl]}zirconium η4-
1,4 diphenyl-1 ,3-butadiene; 9-s lafluorenediylbis! l-[2 -tert-butyl, 4-(2-sec-butylphenyl)indenyl]} zirconium η4-
1,4 •diphenyl-1 ,3-butadiene; 9-s lafluorenediylbis! l-[2 -phenyl, 4-(2-sec-butylphenyl)indenyl]} zirconium η4- 1,4 •diphenyl- 1 ,3-butadiene; 9-s lafluorenediylbis! l-[2 -n-propyl, 4-(2-tert-butylphenyl)indenyl]} zirconium η4- 1,4 •diphenyl- 1 ,3-butadiene; 9-s lafluorenediylbis! 1 -[2-isopropyl, 4-(2-tert-butylphenyl)indenyl] } zirconium η4- 1 ,4-diphenyl- 1,3-butadiene; 9-s lafluorenediylbis! l-[2 -n-butyl, 4-(2-tert-butylphenyl)indenyl]} zirconium η4- 1,4 diphenyl-1 ,3-butadiene; 9-s lafluorenediylbis! 1 -[2-isobutyl, 4-(2-tert-butylphenyl)indenyl] } zirconium η4- 1,4 diphenyl-1 ,3-butadiene; 9-s lafluorenediylbis! 1 -[2-sec-butyl, 4-(2-tert-butylphenyl)indenyl]} zirconium η4- 1,4 diphenyl- 1,3-butadiene; 9-si lafluorenediylbis ! 1 - [2-tert-butyl, 4-(2-tert-butylphenyl)indenyl] } zirconium η4-l ,4-diphenyl-l ,3-butadiene;
9-silafluorenediylbis { l-[2 -phenyl, 4-(2-tert-butylphenyl)indenyl]} zirconium η4- 1 ,4-diphenyl-l ,3-butadiene; 9-silafluorenediylbis! 1 -[2-n-propyl, 4-(2-biphenyl)indenyl]} zirconium η4-l ,4- diphenyl- 1,3-butadiene;
9-silafluorenediylbis! 1 -[2-isopropyl, 4-(2-biphenyl)indenyl]} zirconium η -1,4- diphenyl-1 ,3-butadiene; 9-silafluorenediylbis { 1 - [2-n-butyl, 4-(2-bipheny l)indeny 1] } zirconium η4- 1 ,4- diphenyl- 1,3-butadiene;
9-silafluorenediylbis { 1 -[2-isobutyl, 4-(2-biphenyl)indenyl]} zirconium η4-l ,4- diphenyl-l ,3-butadiene;
9-silafluorenediylbis! 1 -[2-sec-butyl, 4-(2-biphenyl)indenyl]} zirconium η4-l ,4- diphenyl-l ,3-butadiene; 9-silafluorenediylbis {1 -[2-tert-butyl, 4-(2-biphenyl)indenyl]} zirconium η4-l,4- diphenyl- 1 ,3-butadiene;
9-silafluorenediylbis! 1 -[2-phenyl, 4-(2-biphenyl)indenyl]} zirconium η4-l ,4- diphenyl- 1 ,3-butadiene; 9-silafluorenediylbis{ l -[2-n-propyl, 4-(2-α-naphthylphenyl)indenyl]} zirconium η4-l ,4-diphenyl-l ,3-butadiene;
9-silafluorenediylbis { 1 -[2-isopropyl, 4-(2-α-naphthylphenyl)indenyl]} zirconium η4- 1 ,4-diphenyl- 1 ,3-butadiene;
9-silafluorenediylbis! 1 -[2 -n-butyl, 4-(2-α-naphthy lpheny l)indenyl]} zirconium η - 1 ,4-diphenyl-l ,3-butadiene; 9-silafluorenediylbis{ 1 -[2-isobutyl, 4-(2-α-naphthylphenyl)indenyl]} zirconium η4-l,4-diphenyl- 1,3-butadiene;
9-silafluorenediylbis! 1 -[2-sec-butyl, 4-(2-α-naphthylphenyl)indenyl]} zirconium η4- 1 ,4-diphenyl- 1 ,3-butadiene; 9-silafluorenediylbis{l -[2-tert-butyl, 4-(2-α-naphthylphenyl)indenyl]}zirconium η4-l ,4-diphenyl-l ,3-butadiene; 9-silafluorenediylbis{ l-[2 -phenyl, 4-(2-α-naphthylphenyl)indenyl]} zirconium η4-
1 ,4-diphenyl-l ,3-butadiene;
9-silafluorenediylbis! 1 -[2-n-propyl, 4-(2-β-naphthylphenyl)indenyl]} zirconium η4-l ,4-diphenyl-l ,3-butadiene; 9-silafluorenediylbis { 1 -[2-isopropyl, 4-(2-β-naphthy lpheny l)indenyl]} zirconium η4-l,4-diphenyl-l,3-butadiene;
9-silafluorenediylbis { 1 -[2-n-butyl, 4-(2-β-naphthylphenyl)indenyl]} zirconium η4-
1 ,4-diphenyl-l ,3-butadiene;
9-silafluorenediylbis { 1 -[2-isobutyl, 4-(2-β-naphthylphenyl)indenyl]}zirconium η4-l,4-diphenyl- 1,3 -butadiene;
9-silafluorenediylbis {1 -[2-sec-butyl, 4-(2-β-naphthylphenyl)indenyl]} zirconium η4-l ,4-diphenyl-l ,3-butadiene;
9-silafluorenediylbis {1 -[2-tert-butyl, 4-(2-β-naphthylphenyl)indenyl]} zirconium η4-l ,4-diphenyl-l ,3-butadiene; 9-silafluorenediylbis! l-[2 -phenyl, 4-(2-β-naphthylphenyl)indenyl]} zirconium η4-
1 ,4-diphenyl- 1 ,3-butadiene;
9-silafluorenediylbis { 1 - [2-n-propyl, 4-(2 -trifluoromethy lphenyl)indenyl] } - zirconium η4- 1 ,4-diphenyl- 1 ,3-butadiene;
9-silafluorenediylbis! 1 -[2-isopropyl, 4-(2-trifluoromethylphenyl)indenyl]}- zirconium η4-l,4-diphenyl-l,3-butadiene;
9-silafluorenediylbis { 1 - [2-n-butyl, 4-(2 -trifluoromethy lpheny l)indeny 1] } - zirconium η4- 1 ,4-diphenyl- 1 ,3-butadiene;
9-silafluorenediylbis { 1 - [2-isobutyl, 4-(2 -trifluoromethy lphenyl)indenyl] } - zirconium η4- 1 ,4-diphenyl- 1 ,3-butadiene; 9-silafluorenediylbis! 1 -[2-sec-butyl, 4-(2-trifluoromethylphenyl)indenyl]}- zirconium η4-l,4-diphenyl- 1,3-butadiene;
9-silafluorenediylbis{l-[2 -tert-butyl, 4-(2-trifluoromethylphenyl)indenyl]}- zirconium η4-l,4-diphenyl-l,3-butadiene;
9-silafluorenediylbis! 1 -[2-phenyl, 4-(2-trifluoromethylphenyl)indenyl]}- zirconium η4-l,4-diphenyl- 1,3-butadiene; 9-silafluorenediylbis{ 1 -[2-n-propyl, 4-(2,3-dimethylphenyl)indenyl]} zirconium η4-l,4-diphenyl-l,3-butadiene;
9-silafluorenediylbis { 1 -[2-isopropyl, 4-(2,3-dimethylphenyl)indenyl]} zirconium η4-l,4-diphenyl-l,3-butadiene; 9-silafluorenediylbis { l-[2 -n-butyl, 4-(2,3-dimethylphenyl)indenyl]} zirconium η4-
1 ,4-diphenyl-l ,3-butadiene;
9-silafluorenediylbis! 1 -[2-isobutyl, 4-(2,3-dimethylphenyl)indenyl]}zirconium η4-l ,4-diphenyl-l ,3-butadiene;
9-silafluorenediylbis { 1 -[2-sec-butyl, 4-(2,3-dimethylphenyl)indenyl]}zirconium η4-l,4-diphenyl- 1,3-butadiene;
9-silafluorenediylbis! 1 -[2-tert-butyl, 4-(2,3-dimethylphenyl)indenyl]} zirconium η4- 1 ,4-diphenyl- 1 ,3-butadiene;
9-silafluorenediylbis { 1 -[2-phenyl, 4-(2,3-dimethylphenyl)indenyl]}zirconium η4-
1 ,4-diphenyl-l ,3-butadiene; 9-silafluorenediylbis { 1 -[2-n-propyl, 4-(2,3,4-trimethylphenyl)indenyl]}zirconium η4-l,4-diphenyl-l,3-butadiene;
9-silafluorenediylbis { 1 -[2-isopropyl, 4-(2,3,4-trimethylphenyl)indenyl]} zirconium η4- 1 ,4-diphenyl- 1 ,3-butadiene;
9-silafluorenediylbis { 1 -[2-n-butyl, 4-(2,3,4-trimethylphenyl)indenyl]}zirconium η 4- 1 ,4-diphenyl- 1 , 3 -butadiene ;
9-silafluorenediylbis{ l -[2-isobutyl, 4-(2,3, 4-trimethy lphenyl)indenyl]} zirconium η4-l ,4-diphenyl- 1 ,3-butadiene;
9-silafluorenediylbis { 1 -[2-sec-butyl, 4-(2,3,4-trimethylphenyl)indenyl]} zirconium η4- 1 ,4-diphenyl- 1 ,3-butadiene; 9-silafluorenediylbis { 1 -[2-tert-butyl, 4-(2,3,4-trimethylphenyl)indenyl]} zirconium η4-l,4-diphenyl- 1,3-butadiene;
9-silafluorenediylbis { 1 -[2-phenyl, 4-(2,3,4-trimethylphenyl)indenyl]}zirconium η4-l ,4-diphenyl-l ,3-butadiene;
9-silafluorenediy Ibis { 1 -[2-n-propyl, 4-(2, 3, 5-trimethylphenyl)indenyl]} zirconium η4-l,4-diphenyl- 1,3-butadiene; 9-silafluorenediylbis{ 1 -[2-isopropyl, 4-(2,3,5-trimethylphenyl)indenyl]} zirconium η4-l,4-diphenyl- 1,3-butadiene;
9-silafluorenediylbis! l-[2-n-butyl, 4-(2,3,5-trimethylphenyl)indenyl]}zirconium η4- 1 ,4-diphenyl- 1 ,3-butadiene; 9-silafluorenediylbis {1 -[2-isobutyl, 4-(2,3,5-trimethylphenyl)indenyl]} zirconium η4- 1 ,4-diphenyl- 1 ,3-butadiene;
9-silafluorenediylbis{l -[2-sec-butyl, 4-(2,3,5-trimethylphenyl)indenyl]} zirconium η4-l,4-diphenyl-l,3-butadiene;
9-silafluorenediylbis { 1 -[2-tert-butyl, 4-(2,3,5-trimethylphenyl)indenyl]} zirconium η4-l,4-diphenyl- 1,3 -butadiene;
9-silafluorenediylbis{ l -[2-phenyl, 4-(2,3,5-trimethylphenyl)indenyl]}zirconium η4- 1 ,4-diphenyl- 1 ,3-butadiene;
9-silafluorenediylbis { 1 -[2-n-propyl, 4-(2-methylphenyl)indenyl]} hafnium η4-l,4- diphenyl-1 ,3-butadiene; 9-silafluorenediylbis { 1 -[2-isopropyl, 4-(2-methylphenyl)indenyl]} hafnium η4-l ,4- diphenyl-l ,3-butadiene;
9-silafluorenediylbis {1 -[2-n-butyl, 4-(2-methylphenyl)indenyl]}hafnium η4-l,4- diphenyl- 1 ,3-butadiene;
9-silafluorenediylbis! 1 -[2-isobutyl, 4-(2-methylphenyl)indenyl]} hafnium η4-l,4- diphenyl- 1,3-butadiene;
9-silafluorenediylbis! 1 -[2-sec-butyl, 4-(2-methylphenyl)indenyl]}hafnium η4-l,4- diphenyl- 1 ,3-butadiene;
9-silafluorenediylbis! 1 -[2-tert-butyl, 4-(2-methylphenyl)indenyl]} hafnium η4-l,4- diphenyl- 1,3-butadiene; 9-silafluorenediylbis { 1 -[2-phenyl, 4-(2-methy lpheny l)indenyl]} hafnium η4-l ,4- diphenyl- 1 ,3-butadiene;
9-silafluorenediylbis { 1 -[2-n-propyl, 4-(2-ethylphenyl)indenyl]} hafnium η -1,4- diphenyl-1 ,3-butadiene;
9-silafluorenediylbis { 1 -[2-isopropyl, 4-(2-ethy lpheny l)indenyl]} hafnium η4-l ,4- diphenyl- 1,3 -butadiene; 9-silafluorenediylbis ! 1 -[2-n-butyl, 4-(2-ethy lphenyl)indenyl]} hafnium η4- 1,4- diphenyl- 1 ,3-butadiene;
9-silafluorenediylbis { 1 -[2-isobutyl, 4-(2-ethylphenyl)indenyl]} hafnium η4-l,4- diphenyl-1 ,3-butadiene; 9-silafluorenediylbis { 1 -[2-sec-butyl, 4-(2-ethy lpheny l)indenyl]} hafnium η4-l ,4- diphenyl- 1 ,3-butadiene;
9-silafluorenediylbis { 1 -[2-tert-butyl, 4-(2-ethylphenyl)indenyl] }hafnium η4- 1 ,4- diphenyl-l ,3-butadiene;
9-silafluorenediylbis { l-[2 -phenyl, 4-(2-ethy lpheny l)indenyl]} hafnium η4-l ,4- diphenyl-l,3-butadiene;
9-silafluorenediylbis { 1 -[2-n-propyl, 4-(2-n-propylphenyl)indenyl]} hafnium η4-
1 ,4-diphenyl- 1 ,3-butadiene;
9-silafluorenediylbis! 1 -[2-isopropyl, 4-(2 n-propylphenyl)indenyl]} hafnium η4-
1 ,4-diphenyl- 1 ,3-butadiene; 9-silafluorenediylbis! 1 -[2-n-butyl, 4-(2-n-propylphenyl)indenyl]} hafnium η4-l,4- dipheny 1 - 1 ,3-butadiene ;
9-silafluorenediylbis! 1 -[2-isobutyl, 4-(2-n-propylphenyl)indenyl]} hafnium η4-
1 ,4-diphenyl-l ,3-butadiene;
9-silafluorenediylbis! 1 -[2-sec-butyl, 4-(2 -n-propy lphenyl)indenyl]} hafnium η4- l,4-diphenyl-l,3-butadiene;
9-silafluorenediylbis { 1 -[2-tert-butyl, 4-(2-n-propylphenyl)indenyl] }hafnium η4-
1 ,4-diphenyl- 1 ,3-butadiene;
9-silafluorenediylbis! l-[2-phenyl, 4-(2-n-propy lpheny l)indenyl]} hafnium η4- 1,4- diphenyl-1 ,3-butadiene; 9-silafluorenediylbis! 1 -[2-n-propyl, 4-(2-isopropylphenyl)indenyl] } hafnium η4-
1 ,4-diphenyl-l ,3-butadiene;
9-silafluorenediylbis { 1 -[2-isopropyl, 4-(2-isopropylphenyl)indenyl]} hafnium η4-
1 ,4-diphenyl-l,3-butadiene;
9-silafluorenediylbis { l-[2-n-butyl, 4-(2-isopropylphenyl)indenyl]} hafnium η4- 1 ,4-diphenyl- 1,3-butadiene; 9-silafluorenediylbis{ 1 -[2-isobutyl, 4-(2-isopropylphenyl)indenyl]} hafnium η4-
1 ,4-diphenyl-l ,3-butadiene;
9-silafluorenediylbis! 1 -[2-sec-butyl, 4-(2-isopropylphenyl)indenyl]}hafnium η4-
1 ,4-diphenyl-l ,3-butadiene; 9-silafluorenediylbis { l-[2 -tert-butyl, 4-(2-isopropylphenyl)indenyl]} hafnium η4-
1 ,4-diphenyl- 1 ,3-butadiene;
9-silafluorenediylbis { 1 -[2-phenyl, 4-(2-isopropylphenyl)indenyl]}hafnium η4-l,4- diphenyl- 1 ,3-butadiene;
9-silafluorenediylbis { 1 -[2-n-propyl, 4-(2-n-butylphenyl)indenyl]} hafnium η4-l,4- diphenyl- 1,3 -butadiene;
9-silafluorenediylbis { 1 -[2-isopropyl, 4-(2-n-butylphenyl)indenyl]} hafnium η4-
1 ,4-diphenyl- 1 ,3-butadiene;
9-silafluorenediylbis { 1 -[2-n-butyl, 4-(2-n-buty lpheny l)indeny 1] } hafnium η4- 1 ,4- diphenyl-l ,3-butadiene; 9-silafluorenediylbis{ l -[2-isobutyl, 4-(2-n-butylphenyl)indenyl]} hafnium η4-l,4- diphenyl-1 ,3-butadiene;
9-silafluorenediylbis { 1 -[2-sec-butyl, 4-(2-n-butylphenyl)indenyl] } hafnium η4- 1 ,4- diphenyl-l ,3-butadiene;
9-silafluorenediylbis { 1 -[2-tert-butyl, 4-(2-n-butylphenyl)indenyl] } hafnium η4- 1 ,4-diphenyl- 1,3-butadiene;
9-silafluorenediylbis! l-[2 -phenyl, 4-(2-n-butylphenyl)indenyl]} hafnium η4-l ,4- diphenyl- 1,3-butadiene;
9-silafluorenediylbis { 1 -[2-n-propyl, 4-(2-isobuty lpheny l)indenyl]} hafnium η4-
1 ,4-diphenyl- 1 ,3-butadiene; 9-silafluorenediylbis! 1 -[2-isopropyl, 4-(2-isobutylphenyl)indenyl]} hafnium η4-
1 ,4-diphenyl- 1,3-butadiene;
9-silafluorenediylbis {1 -[2-n-butyl, 4-(2-isobuty lphenyl)indenyl]} hafnium η4- 1,4- diphenyl-1 ,3-butadiene;
9-silafluorenediylbis{l-[2-isobutyl, 4-(2-isobutylphenyl)indenyl]}hafnium η4-l,4- diphenyl- 1,3-butadiene; 9-silafluorenediylbis{l -[2-sec-butyl, 4-(2-isobuty lpheny l)indenyl] } hafnium η4-
1 ,4-diphenyl- 1 ,3-butadiene;
9-silafluorenediylbis! 1 -[2-tert-butyl, 4-(2-isobutylphenyl)indenyl]}hafnium η4-
1 ,4-diphenyl-l ,3-butadiene; 9-silafluorenediylbis! 1 -[2-phenyl, 4-(2-isobutylphenyl)indenyl]} hafnium η4-l,4- diphenyl- 1 ,3-butadiene;
9-silafluorenediylbis{l -[2-n-propyl, 4-(2-sec-butylphenyl)indenyl] } hafnium η4-
1 ,4-diphenyl- 1 ,3-butadiene;
9-silafluorenediylbis {1 -[2-isopropyl, 4-(2-sec-butylphenyl)indenyl]} hafnium η - 1 ,4-diphenyl- 1,3-butadiene;
9-silafluorenediylbis {1 -[2 -n-butyl, 4-(2-sec-butylphenyl)indenyl] } hafnium η4- 1,4- diphenyl- 1 ,3-butadiene;
9-silafluorenediylbis {1 -[2-isobutyl, 4-(2-sec-butylphenyl)indenyl]}hafnium η4-
1 ,4-diphenyl-l ,3-butadiene; 9-silafluorenediylbis! 1 -[2-sec-butyl, 4-(2-sec-butylphenyl)indenyl]} hafnium η4-
1 ,4-diphenyl- 1 ,3-butadiene;
9-silafluorenediylbis {1 -[2-tert-butyl, 4-(2-sec-butylphenyl)indenyl]} hafnium η4-
1 ,4-diphenyl- 1 ,3-butadiene;
9-silafluorenediylbis { 1 -[2-phenyl, 4-(2-sec-butylphenyl)indenyl] } hafnium η4- 1,4- diphenyl-l,3-butadiene;
9-silafluorenediylbis! 1 -[2-n-propyl, 4-(2-tert-butylphenyl)indenyl]} hafnium η4-
1 ,4-diphenyl-l ,3-butadiene;
9-silafluorenediylbis {1 -[2-isopropyl, 4-(2-tert-butylphenyl)indenyl]} hafnium η4-
1 ,4-diphenyl- 1 ,3-butadiene; 9-silafluorenediylbis{l -[2-n-butyl, 4-(2-tert-butylphenyl)indenyl]} hafnium η4-
1 ,4-diphenyl-l ,3-butadiene;
9-silafluorenediylbis { 1 -[2-isobutyl, 4-(2-tert-butylphenyl)indenyl] } hafnium η4-
1 ,4-diphenyl- 1 ,3-butadiene;
9-silafluorenediylbis! 1 -[2-sec-butyl, 4-(2 -tert-buty lpheny l)indenyl]} hafnium η4- 1 ,4-diphenyl- 1,3-butadiene; 9-silafluorenediylbis{ 1 -[2-tert-butyl, 4-(2-tert-butylphenyl)indenyl]}hafnium η4-
1 ,4-diphenyl- 1 ,3-butadiene;
9-silafluorenediylbis! 1 -[2-phenyl, 4-(2-tert-butylphenyl)indenyl]}hafnium η4-l,4- diphenyl- 1 ,3-butadiene; 9-silafluorenediylbis { 1 - [2-n-propyl, 4-(2-biphenyl)indenyl] } hafnium η4- 1 ,4- diphenyl- 1 ,3-butadiene;
9-silafluorenediylbis {1 -[2-isopropyl, 4-(2-biphenyl)indenyl]} hafnium η4-l,4- diphenyl- 1 ,3-butadiene;
9-silafluorenediylbis {1 -[2-n-butyl, 4-(2-biphenyl)indeny 1]} hafnium η4- 1,4- diphenyl-l,3-butadiene;
9-silafluorenediylbis { 1 - [2-isobutyl, 4-(2-biphenyl)indenyl] } hafnium η4- 1 ,4- diphenyl- 1 ,3-butadiene;
9-silafluorenediylbis { 1 -[2-sec-butyl, 4-(2-biphenyl)indenyl] } hafnium η4- 1 ,4- diphenyl-l ,3-butadiene; 9-silafluorenediylbis! 1 -[2-tert-butyl, 4-(2-biphenyl)indenyl]}hafnium η4-l,4- diphenyl- 1 ,3-butadiene;
9-silafluorenediylbis { l-[2 -phenyl, 4-(2-biphenyl)indenyl]} hafnium η4-l,4- diphenyl-1 ,3-butadiene;
9-silafluorenediylbis {1 -[2-n-propyl, 4-(2-α-naphthylphenyl)indenyl] } hafnium η4- l,4-diphenyl-l,3-butadiene;
9-silafluorenediylbis! 1 -[2-isopropyl, 4-(2-α-naphthylphenyl)indenyl]} hafnium η4-
1 ,4-diphenyl- 1,3-butadiene;
9-silafluorenediylbis { 1 -[2-n-butyl, 4-(2-α-naphthy lpheny l)indenyl]} hafnium η4-
1 ,4-diphenyl- 1 ,3-butadiene; 9-silafluorenediylbis { 1 -[2-isobutyl, 4-(2-α-naphthylphenyl)indenyl]} hafnium η4-
1 ,4-diphenyl-l ,3-butadiene;
9-silafluorenediylbis {1 -[2-sec-butyl, 4-(2-α-naphthylphenyl)indenyl]}hafnium η4-
1 ,4-diphenyl- 1 ,3-butadiene;
9-silafluorenediylbis { 1 -[2-tert-butyl, 4-(2-α-naphthylphenyl)indenyl]} hafnium η4- 1 ,4-diphenyl- 1,3-butadiene; 9-silafluorenediylbis{ 1 -[2 -phenyl, 4-(2-α-naphthylphenyl)indenyl]}hafnium η4-
1 ,4-diphenyl- 1 ,3-butadiene;
9-silafluorenediylbis! 1 -[2-n-propyl, 4-(2-β-naphthy lpheny l)indenyl]} hafnium η4- l,4-diphenyl-l,3-butadiene; 9-silafluorenediylbis {1 -[2-isopropyl, 4-(2-β-naphthylphenyl)indenyl]}hafnium η4-
1 ,4-diphenyl-l ,3-butadiene;
9-silafluorenediylbis { l-[2 -n-butyl, 4-(2-β-naphthylphenyl)indenyl]} hafnium η4-
1 ,4-diphenyl- 1 ,3-butadiene;
9-silafluorenediylbis { 1 -[2-isobutyl, 4-(2-β-naphthy lpheny l)indenyl]} hafnium η4- 1 ,4-diphenyl- 1,3-butadiene;
9-silafluorenediylbis! 1 -[2-sec-butyl, 4-(2-β-naphthylphenyl)indenyl]}hafnium η4-
1 ,4-diphenyl- 1 ,3-butadiene;
9-silafluorenediylbis { 1 -[2-tert-butyl, 4-(2-β-naphthylphenyl)indenyl]}hafnium η4-
1 ,4-diphenyl-l ,3-butadiene; 9-silafluorenediylbis{l -[2-phenyl, 4-(2-β-naphthylphenyl)indenyl]}hafnium η4-
1 ,4-diphenyl-l ,3-butadiene;
9-silafluorenediylbis {1 -[2-n-propyl, 4-(2 -trifluoromethy lphenyl)indenyl]}- hafnium η4-l ,4-diphenyl-l ,3-butadiene;
9-silafluorenediylbis { 1 -[2-isopropyl, 4-(2-trifluoromethylphenyl)indenyl]}- hafnium η4-l,4-diphenyl- 1,3-butadiene;
9-silafluorenediylbis { 1 -[2-n-butyl, 4-(2-trifluoromethylphenyl)indenyl]} -hafnium η4-l,4-diphenyl-l,3-butadiene;
9-silafluorenediylbis! 1 -[2-isobutyl, 4-(2-trifluoromethylphenyl)indenyl]} -hafnium η4- 1 ,4-diphenyl- 1 ,3-butadiene; 9-silafluorenediylbis { 1 -[2-sec-butyl, 4-(2-trifluoromethylphenyl)indenyl]}- hafnium η -l,4-diphenyl-l,3-butadiene;
9-silafluorenediylbis ! 1 -[2-tert-butyl, 4-(2-trifluoromethylphenyl)indenyl] } - hafnium η4-l,4-diphenyl-l,3-butadiene;
9-silafluorenediylbis { 1 -[2-phenyl, 4-(2-trifluoromethylphenyl)indenyl]} -hafnium η4-l,4-diphenyl-l,3-butadiene; 9-silafluorenediylbis{ 1 -[2-n-propyl, 4-(2,3-dimethylphenyl)indenyl]}hafnium η4-
1 ,4-diphenyl- 1,3-butadiene;
9-silafluorenediylbis{ l-[2-isopropyl, 4-(2,3-dimethylphenyl)indenyl]} hafnium η -
1 ,4-diphenyl- 1 ,3-butadiene; 9-silafluorenediylbis {1 -[2-n-butyl, 4-(2,3-dimethylphenyl)indenyl]}hafnium η4-
1 ,4-diphenyl-l ,3-butadiene;
9-silafluorenediylbis! 1 -[2-isobutyl, 4-(2,3-dimethylphenyl)indenyl]}hafnium η4-
1 ,4-diphenyl-l ,3-butadiene;
9-silafluorenediylbis! 1 -[2-sec-butyl, 4-(2,3-dimethylphenyl)indenyl] }hafnium η4- 1 ,4-diphenyl- 1,3-butadiene;
9-silafluorenediylbis {1 -[2-tert-butyl, 4-(2,3-dimethylphenyl)indenyl]}hafnium η4-
1 ,4-diphenyl- 1,3-butadiene;
9-silafluorenediylbis {1 -[2-phenyl, 4-(2,3-dimethylphenyl)indenyl]}hafnium η4-
1 ,4-diphenyl- 1,3-butadiene; 9-silafluorenediylbis {1 -[2-n-propyl, 4-(2,3,4-trimethylphenyl)indenyl]}hafnium η4- 1 ,4-diphenyl- 1 ,3-butadiene;
9-silafluorenediylbis { 1 -[2-isopropyl, 4-(2, 3, 4-trimethy lpheny l)indenyl]} hafnium η4- 1 ,4-diphenyl- 1 ,3-butadiene;
9-silafluorenediylbis! 1 -[2-n-butyl, 4-(2,3,4-trimethylphenyl)indenyl]}hafnium η4- l,4-diphenyl-l,3-butadiene;
9-silafluorenediylbis! 1 -[2-isobutyl, 4-(2,3,4-trimethylphenyl)indenyl]}hafnium η4- 1 ,4-diphenyl- 1 ,3-butadiene;
9-silafluorenediylbis { 1 -[2-sec-butyl, 4-(2,3,4-trimethylphenyl)indenyl]} hafnium η4-l ,4-diphenyl-l ,3-butadiene; 9-silafluorenediylbis { 1 -[2-tert-butyl, 4-(2,3, 4-trimethy lphenyl)indenyl]} hafnium η4-l ,4-diphenyl-l ,3-butadiene;
9-silafluorenediylbis{ 1 -[2-phenyl, 4-(2,3,4-trimethylphenyl)indenyl]}hafnium η4-
1 ,4-diphenyl-l ,3-butadiene;
9-silafluorenediylbis! 1 -[2-n-propyl, 4-(2,3,5-trimethylphenyl)indenyl]}hafnium η4- 1 ,4-diphenyl- 1 ,3-butadiene; 9-silafluorenediylbis{ 1 -[2-isopropyl, 4-(2,3,5-trimethylphenyl)indenyl]} hafnium η4- 1 ,4-diphenyl-l ,3-butadiene;
9-silafluorenediylbis { 1 -[2-n-butyl, 4-(2,3,5-trimethylphenyl)indenyl]}hafnium η4- 1 ,4-diphenyl- 1 ,3-butadiene; 9-silafluorenediylbis { 1 -[2-isobutyl, 4-(2,3,5-trimethylphenyl)indenyl]}hafnium η4- 1 ,4-diphenyl- 1 ,3-butadiene;
9-silafluorenediylbis {1 -[2-sec-butyl, 4-(2,3,5-trimethylphenyl)indenyl]} hafnium η4-l,4-diphenyl- 1,3-butadiene;
9-silafluorenediylbis {1 -[2 -tert-butyl, 4-(2,3,5-trimethylphenyl)indenyl]} hafnium η4-l,4-diphenyl- 1,3-butadiene; and
9-silafluorenediylbis { 1 -[2-phenyl, 4-(2,3,5-trimethylphenyl)indenyl]}hafnium η4- 1 ,4-diphenyl- 1 ,3-butadiene.
The above names represent the individual stereoisomers as well as mixtures of any ratios thereof. For example, "dimethylsilanediylbis! 1 -[2-n-propyl,
4-(2 -methy lphenyl)indenyl]} zirconium dichloride" represents rac- dimethylsilanediylbis! l -[2-n-propyl, 4-(2-methy lpheny l)indenyl]} zirconium dichloride, meso- dimethylsilanediylbis! 1 -[2-n-propyl, 4-(2- methylphenyl)indenyl]} zirconium dichloride and any mixtures of these compounds.
Moreover, "biphenylyl" in the above names is synonymous with "phenylphenyl".
"9-silafluorenediyl-" refers to a group of the following formula:
Figure imgf000170_0001
The metallocenes of this invention are prepared according to general techniques known from the literature, for example U.S. Patent Nos. 5,789,634 and 5,840,644 (both fully incorporated herein by reference).
Generally, metallocenes of this type are synthesized as shown below (for R =H) where (a) is an aryl-coupling reaction between a 4-halosubstituted indene and an aryl Grignard reagent catalyzed by NiCl2(PPh3)2 in ether-type solvents at room temperature to reflux. Product is usually purified by column chromatography or distillation, (b) is a deprotonation via a metal salt of an alkyl anion (e.g. n-BuLi) to form an indenide followed by reaction with an appropriate bridging precursor (e.g. Me2SiCl2). Reactions are usually done in ether-type solvents at ambient temperatures. The final product is purified by column chromatography or distillation; and (c) is double deprotonation via an alkyl anion (e.g. n-BuLi) to form a dianion followed by reaction with a metal halide (e.g.
ZrCl4).The reactions are usually done in ether-type or aromatic solvents at ambient temperatures. The final products are obtained by recrystallization of the crude solids. 169-
Figure imgf000171_0001
The metallocenes of this invention are highly active catalyst components for the polymerization of olefins. They can form different stereoisomers and are preferably employed as chiral racemates. However, it is also possible to use the individual enantiomers in the (+) or (-) form. The individual stereoisomers allow - an optically active polymer to be prepared. In some cases it may be desirable to remove the meso form of the metallocenes, since the polymerization-active center (the metal atom) in these compounds is no longer chiral due to the mirror symmetry at the central metal atom and it is, therefore, not possible to produce a highly isotactic polymer. If the meso form is not removed, atactic polymer is formed in addition to isotactic polymer. For certain applications (e.g., if a random copolymer of propylene and ethylene and/or any other monoolefin and/or diene is to be made) this may be entirely desirable. Accordingly, racemic metallocenes contaminated with not more than about 5 %, preferably not more than about 2 %, and even more preferred not more than about 1%, of the meso form represent a particularly preferred embodiment of the metallocenes of the present invention. In another preferred embodiment, the meso form of a metallocene of the present invention is contaminated with not more than about 5 %, preferably not more than about 2 %, and even more preferred not more than about 1%, of the racemic form.
Rac/meso metallocene isomer separation is facilitated when metallocenes containing certain bridging groups are prepared. This has been found to be true when the bridging group, R , is represented by the formula:
Figure imgf000172_0001
wherein M2 and R17 to R24 are as defined above. Metallocenes are generally used in combination with some form of activator in order to create an active catalyst system. The terms "activator" and
"cocatalyst" are used interchangeably and are defined herein to mean any compound or component, or combination of compounds or components, capable of enhancing the ability of one or more metallocenes to polymerize olefins.
Alkylalumoxanes such as methylalumoxane (MAO) are commonly used as metallocene activators. The alumoxanes which may be employed according to the present invention are not particularly limited. They include oligomeric linear and/or cyclic alkylalumoxanes of the general formula R-(Al(R)-O)n-AlR2 for oligomeric, linear alumoxanes and (-Al(R)-O-)m for oligomeric cyclic alumoxanes wherein n usually is 1-40, preferably 10-20, m usually is 3-40, preferably 3-20, and R usually is a CpC8 alkyl group (e.g., methyl, ethyl, n-propyl, isopropyl, n- butyl and isobutyl), and preferably methyl to provide methylalumoxane (MAO). MAO is a mixture of oligomers with a very wide distribution of molecular weights and usually with an average molecular weight of about 1200. MAO is typically kept in solution in toluene. It is also possible to use, for the present purpose, alumoxanes of the type just described wherein the alkyl groups in the above general formulae are different. A preferred example thereof is modified methylalumoxane (MMAO) wherein in comparison to MAO a part of the methyl groups is replaced by other alkyl groups. Alumoxane solutions, particularly methylalumoxane solutions, may be obtained from commercial vendors as solutions having various concentrations. There are a variety of methods for preparing alumoxane, non-limiting examples of which are described in U.S. Patent Nos. 4,665,208, 4,952,540, 5,091 ,352, 5,206,199, 5,204,419, 4,874,734,
4,924,018, 4,908,463, 4,968,827, 5,308,815, 5,329,032, 5,248,801, 5,235,081 , 5,103,031 , 6,001 ,766 and EP-A-0 561 476, EP-B1-0 279 586, EP-A-0 594-218 and WO 94/10180, each fully incorporated herein by reference.
Generally the atomic ratio of Al in the alumoxane to metal in the metallocene compound is at least about 10 : 1 , more preferably at least about 50 : 1 , and most preferred at least about 80 : 1. On the other hand said ratio is generally not higher than about 1 ,000 : 1 , particularly not higher than about 500 : 1, with a ratio of not higher than about 300 : 1 being particularly preferred.
Ionizing activators may also be used to activate metallocenes. These activators are neutral or ionic, or are compounds such as tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, which ionize the neutral metallocene compound. Unlike alumoxane cocatalysts, these ionizing activators can usually be employed in a molar ratio with respect to the metallocene which is much closer to 1 :1 (e.g., less than 5:1, less than 2:1, and preferably about 1 :1). Such ionizing compounds may contain an active proton, or some other cation associated with, but not coordinated or only loosely coordinated to, the remaining ion of the ionizing compound. Combinations of activators may also be used, for example, alumoxane and ionizing activator combination, see for example, WO 94/07928 (incorporated herein by reference in its entirety).
Descriptions of ionic catalysts for coordination polymerization comprised of metallocene cations activated by noncoordinating anions appear in the early work in EP-A-0 277 003, EP-A-0 277 004 and U.S. Patent No. 5,198,401 and WO-A-92/00333 (each fully incorporated herein by reference). These teach desirable methods of preparation wherein metallocenes are protonated by an anion precursor such that an alkyl/hydride group is abstracted from a transition metal to make it both cationic and charge-balanced by the non-coordinating anion. Suitable ionic salts include tetrakis-substituted borate or aluminum salts having fluorinated aryl -constituents such as phenyl, biphenyl and naphthyl.
The term "noncoordinating anion" (NCA) means an anion which either does not coordinate to said cation or which is only weakly coordinated to said cation thereby remaining sufficiently labile to be displaced by a neutral Lewis base. "Compatible" non-coordinating anions are those which are not degraded to neutrality when the initially formed complex decomposes. Further, the anion will not transfer an anionic substituent or fragment to the cation so as to cause it to form a neutral four coordinate metallocene compound and a neutral by-product from the anion. Non-coordinating anions useful in accordance with this invention are those which are compatible, stabilize the metallocene cation in the sense of balancing its ionic charge at +1, yet retain sufficient lability to permit displacement by an ethylenically or acetylenically unsaturated monomer during polymerization.
The use of ionizing ionic compounds not containing an active proton but capable of producing both the active metallocene cation and a non-coordinating anion is also known. See, for example, EP-A-0 426 637 and EP-A- 0 573 403 (each fully incorporated herein by reference). An additional method of making the ionic catalysts uses ionizing anion precursors which are initially neutral Lewis acids but form the cation and anion upon ionizing reaction with the metallocene compounds, for example the use of tris(pentafluorophenyl)borane. See EP-A-0 520732 (incorporated herein by reference in its entirety). Ionic catalysts for addition polymerization can also be prepared by oxidation of the metal centers of transition metal compounds by anion precursors containing metallic oxidizing groups along with the anion groups, see EP-A-0 495 375 (fully incorporated herein by reference).
Where the metal ligands include halogen moieties (for example, chloride) which are not capable of ionizing abstraction under standard conditions, they can be converted via known alkylation reactions with organometallic compounds such as lithium or aluminum hydrides or alkyls, alkylalumoxanes, Grignard reagents, etc. See EP-A-0 500 944 and EP-A1-0 570 982 (each fully incorporated herein by reference) for in situ processes describing the reaction of alkyl aluminum compounds with dihalo-substituted metallocene compounds prior to or with the addition of activating anionic compounds.
Methods for supporting ionic catalysts comprising metallocene cations and NCAs are described in WO 9950311, U.S. Patent Nos. 5,643,847 and 5,972,823,
U.S. Patent Application No. 09/184358, filed November 2, 1998 and U.S. Patent Application No. 09/184389, filed November 2, 1998 (each fully incorporated herein by reference).
When the activator for the metallocene supported catalyst composition is a NCA, preferably the NCA is first added to the support composition followed by the addition of the metallocene catalyst. When the activator is MAO, preferably the MAO and metallocene catalyst are dissolved together in solution. The support is then contacted with the MAO/metallocene catalyst solution. Other methods and orders of addition will be apparent to those skilled in the art.
The catalyst compositions of this invention preferably comprise a support. Suitable supports include porous particulate materials, such as for example, talc, inorganic oxides, inorganic chlorides such as magnesium chloride, and resinous materials such as polyolefins or other polymers.
Preferably, the support materials are porous inorganic oxide materials, which include those from the Periodic Table of Elements of Groups 2, 3, 4, 5, 13 or 14 metal/metalloid oxides. Silica, alumina, silica-alumina, and mixtures thereof are particularly preferable. Other inorganic oxides that may be employed either alone or in combination with the silica, alumina or silica-alumina are magnesia, titania, zirconia, and the like.
In one preferred embodiment the support material is porous silica, more preferably porous silica which has a surface area in the range of not less than 10, preferably not less than 50, and most preferred not less than 100 m2/g , but usually not more than 700, preferably not more than 500, and most preferred not more than 400 m2/g. The total pore volume thereof usually is not less than 0.1, preferably not less than 0.5, and most preferred not less than 0.8 cc/g, whereas the pore volume generally is not higher than 4.0, preferably not higher than 3.5, most preferred not higher than 3.0 cc/g. The average particle size of the porous silica should be at least 10, preferably at least 20, and most preferred at least 30 μm, the maximum value thereof usually being not higher than 500, preferably not higher than 200, and most preferred not higher than 100 μm. The average pore size of typical porous support materials usually is at least 10, preferably at least 50, and even more preferably at least 75 A. Average pore sizes should generally not be higher than 1000, preferably not higher than 500, and most preferred not higher than 350 A. It may be particularly desirable to dehydrate the silica at a temperature of from 100°C to 800°C anywhere from 3 to 24 hours.
The metallocene, activator and support material may be combined in any number of ways. More than one metallocene may also be used. Examples of suitable support techniques are described in U. S. Patent Nos. 4,808,561 and
4,701,432 (each fully incorporated herein by reference). Preferably metallocene and activator are combined and their contact product is supported on the porous support material as described in U. S. Patent No. 5,240,894 and WO 94/28034, WO 96/00243, and WO 96/00245 (each fully incorporated herein by reference). Alternatively, the metallocenes may be preactivated separately and then combined with the support material either separately or together. If the metallocenes are separately supported, then preferably, they are dried and then combined as a powder before use in polymerization.
Regardless of whether the metallocene(s) and their activator are separately precontacted or whether the metallocene(s) and activator are combined at once, in some instances it may be preferred that the total volume of reaction solution applied to the porous support is less than 4 times the total pore volume of the porous support, more preferably less than 3 times the total pore volume of the porous support and even more preferably in the range of from more than 1 to less than 2.5 times the total pore volume of the porous support. Procedures for measuring the total pore volume of porous support are well known in the art. One such method is described in Volume 1, Experimental Methods in Catalyst Research, Academic Press, 1968, pages 67-96, fully incorporated herein by reference. The supported catalyst system may be used directly in polymerization or the catalyst system may be prepolymerized using methods well known in the art.
For details regarding prepolymerization, see U. S. Patent Nos. 4,923,833 and
4,921,825, and EP 0 279 863 and EP 0 354 893 (each fully incorporated herein by reference).
The metallocene catalyst systems described herein are useful in the polymerization of all types of olefins. This includes polymerization processes which produce homopolymers, copolymers, terpolymers and the like as well as block copolymers and impact copolymers. These polymerization processes may be carried out in solution, in suspension or in the gas phase, continuously or batchwise, or any combination thereof, in one or more steps, usually at a temperature not lower than 30, preferably not lower than 50, most preferred not lower than 80° C, and not higher than 200, preferably not higher than 120, most preferred not higher than 100°C. Preferably, the polymerization or copolymerization is carried out using olefins of the formula Ra-CH=CH-Rb . In this formula, Ra and Rb are identical or different and are a hydrogen atom or an alkyl or alkenyl radical having 1 to 14 carbon atoms. Alternatively, Raand Rb may form a ring together with the carbon atoms connecting them. Examples of such olefins are ethylene, propylene, 1-butene, 1-hexene, 4-methyl-l-pentene, and 1- octene, vinylcyclohexane, norbornene and norbornadiene. In particular, propylene and ethylene are polymerized. The metallocenes and metallocenes catalyst systems of this invention are most suitable for the polymerization of propylene based polymers.
If necessary, hydrogen is added as a molecular-weight regulator and/or in order to increase the activity. The overall pressure in the polymerization system usually is at least about 0.5 bar, preferably at least about 2 bar, most preferred at least about 5 bar. Pressures higher than about 100, e.g., higher than about 80 bar and, in particular, higher than about 64 bar are usually not preferred. Typically, the metallocene is used in the polymerization in a concentration, based on the transition metal, of not less 10"4, preferably not less than 10"3 mol, and not higher than 107, preferably not higher than 104 mol, of transition metal per dm of solvent or per dm of reactor volume. When alumoxane is used as the cocatalyst, it is used in a concentration of usually not less than 10"4 ,preferably not less than 10" mol, and not higher than 10" , preferably not higher than 10" mol, per dm of solvent or per dm of reactor volume. The other cocatalysts mentioned are used in an approximately equimolar amount (e.g., from about 1.2 : 1 to about 1 : 1.2) with respect to the metallocene. In principle, however, higher concentrations are also possible.
If the polymerization is carried out as a suspension or solution polymerization, an inert solvent which is customary for the Ziegler low-pressure process is typically used for example, the polymerization is carried out in an aliphatic or cycloaliphatic hydrocarbon; examples of which are propane, butane, hexane, heptane, isooctane, cyclohexane and methylcyclohexane. It is also possible to use mineral spirit or a hydrogenated diesel oil fraction. Toluene can also be used. The polymerization is preferably carried out in the liquid monomer(s). If inert solvents are used, the monomer(s) is (are) metered in gas or liquid form.
Before addition of the catalyst, in particular of the supported catalyst system, another alkylaluminum compound, such as, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum or isoprenylaluminum, may additionally be introduced into the reactor in order to render the polymerization system inert (for example to remove catalyst poisons present in the olefin). This compound is added to the polymerization system in a concentration of from 100 to 0.01 mmol of Al per kg of reactor contents. Preference is given to triisobutylaluminum and triethylaluminum in a concentration of from 10 to 0.1 mmol of Al per kg of reactor contents. This allows the molar Al/M1 ratio to be selected at a low level in the synthesis of a supported catalyst system. In principle, however, the use of further substances for catalysis of the polymerization reaction is unnecessary, i.e., the systems according to the invention can be used as the only catalysts for the polymerization of olefins.
The process according to the invention is distinguished by the fact that the metallocenes described can give propylene polymers of very high molecular weight, melting point, and very high stereotacticity, with high catalyst activities in, e.g., the temperature range from about 40°C to about 100°C, such as the industrially particularly interesting polymerization temperature range of from about 50°C to about 80°C .
The catalyst systems of this invention are capable of providing polymers, particularly propylene homopolymers and copolymers, of exceptionally high molecular weight and melting point even when used in processes under commercially relevant conditions of temperature, pressure and catalyst activity.
Preferred melting points of olefin polymers comprising at least about 99 % by weight, preferably are at least about 99.3 % by weight and most preferred at least 99.5 % by weight of units derived from propylene (the remainder being preferably derived from one or more compounds selected from ethylene and 1 -olefins comprising 4 to 12 carbon atoms, most preferred ethylene) are as high as 155°C, e.g., as high as 156°C, more preferably at least 157°C, even more preferably at least 158°C, and may be as high as 160°C or even higher (these melting points being determined by DSC according to the procedure described in the Examples below).
With respect to molecular weights, copolymers made with the catalyst systems of the present invention such as, e.g., ethylene/propylene rubbers (EPR's) or ethylene/propylene/diene copolymers (EPDM's), usually have an intrinsic viscosity, measured in decalin at 135° C, of usually at least about 1.8, preferably at least about 2.0, and more preferred at least about 2.1 (e.g., at least about 2.2). This enables the production of very satisfactory impact copolymers (ICP's), such as in situ blends of propylene homopolymer or copolymer as discussed above of high melting point (and preferably also high molecular weight) and propylene copolymers (such as EPR's and/or EPDM's) of high intrinsic viscosity with a single catalyst system (and, preferably, in a single reactor). For this purpose, the copolymers generally will have an ethylene content of at least about 30, preferably at least about 35, more preferred at least about 40 weight % and not more than about 60, preferably not more than about 50 weight %. The ethylene content of the ICP's usually will be at least about 1.5, preferably at least about 3 weight percent and up to about 20, preferably up to about 15, weight %.
The homo- and copolymers made with the catalyst systems of the present invention (e.g., those containing units derived from propylene, or from propylene and ethylene) also have a narrow molecular weight distribution, Mw/Mn, usually of not higher than about 3.5, preferably not higher than about 3.0, more preferred not higher than about 2.5 and sometimes even not higher than about 2.2. They also are distinguished by low xylene and n-hexane extractables contents. Often the xylene extractables and/or the n-hexane extractables of these homo- and copolymers will amount to less than about 2.0, preferably less than about 1.5, even more preferred less than about 1.0 weight %. A general description of the procedure for measuring the xylene extractables (solubles) is found in J. C. Randall, J. Poly.
Sci.: Part A Polymer Chemistry, Vol. 36, 1527-1542 (1998), incorporated herein by reference in its entirety. Hexane extractions are performed by weighing the polymer sample in a dried soxhlet thimble. Hexane is heated to reflux through the thimble in the soxhlet apparatus. When the extraction is complete the solvent is evaporated, and the sample dried under the appropriate vacuum. The amount of extractables is determined by weight.The thimble containing the insoluble polymer is dried in a vacuum oven and the weight of the recovered polymer is determined.
The polymer compositions of the present invention are also characterized by a relatively narrow molecular weight distribution. Their values of Mw/Mn (as determined by Gel Permeation Chromatography using polystyrene standards, see Examples below) usually are not higher than about 3.5, often not higher than about 3.0, e.g., not higher than about 2.7.
Catalyst systems of this invention are capable of providing propylene polymers having high stereospecificity and regiospecificity. Isotactic propylene polymers prepared according to the processes of this invention may have a proportion of 2,1 -inserted propene units of less than about 0.5%, at a triad tacticity of greater than about 98% (see, for example, the results summarized in Table 21C, below). Preferably, there is no measurable proportion of 2,1 -inserted propene units. Triad tacticity is determined using C-NMR according to J.C. Randall,
Polymer Sequence Determination: Carbon-13 NMR Method, Academic Press New York 1978, incorporated herein by reference in its entirety.
Polymers prepared using the processes described herein find uses in all applications including fibers, injection-molded parts, films, pipes, and wire and cable applications. Non-limiting examples include carpet fibers and primary and secondary carpet backing; slit tape applications such as tarpaulins, erosion abatement screens, sand bags, fertilizer and feed bags, swimming pool covers, intermediate bulk container (IBC) bags; non-woven applications for spunbonded, melt blown and thermobonded carded web applications such as disposable diaper liners, feminine hygiene products, tarpaulins and tent fabrics, and hospital garments; apparel applications such as socks, T-shirts, undergarments, bicycle shorts, sweat bands, football undershirts, hiking socks and other outdoor sporting apparel; cordage applications such as mooring and towing lines and rope applications; netting applications such as safety fences, geogrids for soil stabilization; injection molded applications such as appliance parts in automatic dishwashers and clothes washers, hand tools and kitchen appliances; consumer product applications such as outdoor furniture, luggage, infant car seats, ice coolers, yard equipment; medical applications such as disposable syringes and other hospital and laboratory devices; rigid packaging made by injection molding, blow molding or thermoforming such as margarine tubs, yogurt containers and closures, commercial bottles and ready-to-eat food containers; transportation applications such as automotive interior trim, instrument panels, bumper fascia, grills and external trim parts, battery cases; film applications such as snack packages and other food packaging and film labels, packing tapes and pressure sensitive labels; wire and cable applications such as wire insulation .
While the present invention has been described and illustrated by reference to particular embodiments, it will be appreciated by those of ordinary skill in the art, that the invention lends itself to many different variations not illustrated herein. For these reasons, then, reference should be made solely to the appended claims for purposes of determining the true scope of the present invention.
Although the appendant claims have single appendencies in accordance with U.S. patent practice, each of the features in any of the appendant claims can be combined with each of the features of other appendant claims or the main claim.
EXAMPLES
All air sensitive experiments were carried out in nitrogen purged dry boxes. All solvents were purchased from commercial sources. Aluminum alkyls were purchased as hydrocarbon solutions from commercial sources. The commercial methylalumoxane ("MAO") was purchased from Albemarle as a 30 wt % solution in toluene.
EXAMPLE 1
Racemic dimethylsilanediylbis! 1 -[2-methyl, 4-phenylindenyl]} zirconium dichloride was obtained from commercial sources and used as received. Supported Metallocene Catalyst System 1
In a 100 mL round bottom flask racemic dimethylsilanediylbis! 1 -[2- methyl, 4-phenylindenyl]} zirconium dichloride (0.055 g) was added to the above MAO solution (6.74 g, 7.2 mL) and stirred twenty minutes. The resultant mixture was filtered through a medium glass frit funnel and washed with toluene (14 mL).
To the combined filtrates was added dehydrated silica (4.0 g, Davison 948 Regular, 600°C dehydration). This slurry was stirred for twenty minutes then dried at 40 °C for two minutes under vacuum on a rotary evaporator until the liquid evaporated and then the solid was further dried a total of about 2 hours and twenty two minutes. The supported catalyst was recovered as a light orange, free flowing solid (5.63 g).
EXAMPLE 2
2-Methyl, 4-(3 -methy lpheny l)-indene 3-Bromotoluene (10.0 g, 58 mmol) and magnesium turnings (2.0 g, 83 mmol) were taken up in 150 mL of Et O (diethyl ether) and stirred at room temperature overnight to form the Grignard solution. In a separate flask,
NiCl2(PPh3)2 (1.8 g, 2.8 mmol) and 4-chloro-2-methylindene (9.5 g, 58 mmol) were dissolved in 150 mL of Et2O. The Grignard solution was added dropwise to this solution and allowed to stir overnight at reflux. After overnight stirring, the reaction was slowly quenched with H2O to neutralize unreacted Grignard. The solution was subsequently treated with 100 mL of 10% HCl(aq), and neutralized with saturated sodium bicarbonate aqueous solution. The organic layer was dried with magnesium sulfate and the solvent removed by rotary evaporation. The remaining residue was loaded onto a silica gel column and eluted with hexane.
Yield: 6.3 g (48 %).
Lithium! 1 -[2-methyl, 4-(3-methylphenyl)indenide]} 2-Methyl, 4-(3-methylphenyl)-indene (6.3 g, 28 mmol) was dissolved in 100 mL of pentane. To this solution was added 11 mL of n-BuLi (n-butyl lithium;
2.5M in hexane) and the reaction was allowed to stir 5 hours at room temperature. A yellow-white solid precipitated from the solution and was collected by frit filtration and washed with additional pentane. Yield: 6.0 g (95%).
Dimethylsilanediylbis! 1 -[2-methyl, 4-(3 -methy lpheny l)indene]} Me2SiCl2 (dichlorodimethylsilane; 0.83 g, 6.5 mmol) was dissolved in 80 ml of THF. While stirring, lithium! 1 -[2-methyl, 4-(3-methylphenyl)indenide]} (3.0 g, 13 mmol) was added as a dry powder and the contents were allowed to stir at reflux overnight. The solvent was removed in vacuo and the residue was taken up in pentane and filtered to remove LiCl salts. The pentane was removed in vacuo, and the crude product was isolated. Yield: 2.4 g (74 %)
Dimethylsilanediylbis! l-[2-methyl,4-(3-methylphenyl)indenyl]} zirconium dichloride
Dimethylsilanediylbis{l-[2-methyl,4-(3-methylphenyl)indene]} (2.4 g, 4.6 mmol) was dissolved in 50 mL of Et2O. To this solution was added 3.7 mL of n-
BuLi (2.5M in hexane) and stirred for 3 hours. The solution was then cooled to
-35 °C and ZrCl4 (1.1 g, 5.9 mmol) was added as a dry powder and the reaction was stirred at room temperature overnight. The solvent was removed in vacuo and the residue was taken up in toluene. The solution was filtered through a celite packed frit to remove LiCl, concentrated and cooled to -35 °C to induce crystallization. Yellow-orange crystals of the racemic isomer were isolated.
Yield: 260 mg (8.6%).
Supported Metallocene Catalyst System 2 In a 100 mL round bottom flask dimethylsilanediylbis { 1 -[2-methyl, 4-(3- methylphenyl)indenyl]} zirconium dichloride (0.058 g) was added to the above MAO-toluene solution (6.74 g) and stirred twenty minutes. The resultant mixture was filtered through a medium glass frit funnel and washed with toluene (14 mL). To the combined filtrates were added dehydrated silica (4.0 g, Davison 948 Regular, 600°C dehydration). This slurry was stirred for twenty minutes, then dried at 40 °C for two minutes under vacuum on a rotary evaporator until the liquid evaporated and then the solid was further dried a total of about 2 hours and twenty nine minutes. The supported catalyst was recovered as a reddish orange, free flowing solid (5.58 g).
EXAMPLE 3 2 -Methyl, 4-(3,5-dimethylphenyl)-indene
4-Chloro-2-methylindene (8.9 g, 54 mmol) and NiCl2(PPh3)2 (1.8g, 2.8 mmol) were dissolved in 150 mL of Et O. 3,5-Dimethylphenylmagnesium bromide (lOg, 54 mmol) as Et2O solution was added to the solution and the reaction was stirred overnight at room temperature. After overnight stirring the reaction was slowly quenched with H2O to neutralize unreacted Grignard. The solution was subsequently treated with 100 mL of 10% HCl(aq), and neutralized with saturated sodium bicarbonate aqueous solution. The organic layer was dried with magnesium sulfate and the solvent was removed by rotary evaporation. The remaining residue was loaded onto a silica gel column and eluted with hexane. Yield: 5.6 g (44%).
Lithium ! 1 - [2-methyl, 4-(3 ,5 -dimethy lphenyl)indenide] }
2-Methyl, 4-(3,5-dimethylphenyl)-indene (5.6 g, 23.9 mmol) was dissolved in 80 mL of pentane. To this solution was added 9.6 mL of n-BuLi (2.5M in hexane) and the reaction was allowed to stir 4 hours at room temperature. A white solid precipitated from solution and was collected by frit filtration and washed with additional pentane. Yield: 4.5 g (80 %).
Dimethylsilanediylbis! 1 -[2-methyl, 4-(3,5-dimethylphenyl)indene]} Me2SiCl2 (1.2 g, 9.4 mmol) was dissolved in 80 mL of THF. While stirring, lithium! 1 -[2-methyl, 4-(3,5-dimethylphenyl)indenide]} (4.5 g, 18.7 mmol) was added as a dry powder and the contents were allowed to stir overnight at room temperature. The solvent was removed in vacuo and the residue was taken up in pentane and filtered to remove LiCl salts. The pentane was removed in vacuo to yield a flaky white solid (4.23 g, 87 %). Dimethylsilanediylbis! 1 -[2-methyl, 4-(3,5-dimethylphenyl)indenyl]} zirconium dichloride
Dimethylsilanediylbis! 1 -[2-methyl, 4-(3,5-dimethylphenyl)indene]} (4.23 g, 8.0 mmol) was dissolved in 60 mL of Et2O. While stirring, 6.4 mL of n-BuLi (2.5M in hexane) was added and allowed to stir at room temperature for 2 hours.
After this time, the solution was cooled to -35 °C and ZrCl4 (1.58 g, 8.0 mmol) was added and allowed to stir at room temperature for 3 hours. The solvent was then removed in vacuo and the residue was taken up in a mixture of methylene chloride and pentane and filtered to remove LiCl salts. The filtrate was then concentrated and chilled to -35 °C to induce crystallization. 0.23 g (5.0%) of pure racemic compound was obtained.
Supported Metallocene Catalyst System 3
In a 100 mL round bottom flask dimethylsilanediylbis! 1 -[2-methyl, 4- (3,5-dimethylphenyl)indenyl]}zirconium dichloride (0.061 g) was added to the above MAO-toluene solution (6.74 g, 7.35 mL) and stirred twenty minutes. The resultant mixture was filtered through a medium glass frit funnel and washed with toluene (14 mL). To the combined filtrates was added dehydrated silica (4.0 g, Davison 948 Regular, 600°C dehydration). This slurry was stirred for twenty minutes, then dried at 40 °C for two minutes under vacuum on a rotary evaporator until the liquid evaporated and then the solid was further dried a total of about two hours and twenty six minutes. The supported catalyst was recovered as a light orange, free flowing solid (5.36 g).
EXAMPLE 4
2-Methyl, 4-(2-methylphenyl)-indene 2-Bromotoluene (8.8 g, 51 mmol) and magnesium turnings (2.4 g, 102 mmol) were taken up in 100 mL of Et2O (diethyl ether) and stirred at room temperature for 4 hours to form the Grignard solution. In a separate flask, NiCl2(PPh3)2 (1.8 g, 2.8 mmol) and 4-chloro-2-methylindene (8.4 g, 51 mmol) were dissolved in 300 mL of Et2O. The Grignard solution was added dropwise to this solution and allowed to stir overnight at reflux. After overnight stirring, the reaction was slowly quenched with H2O to neutralize unreacted Grignard. The solution was subsequently treated with 100 mL of 10% HCl(aq) and neutralized with saturated sodium bicarbonate aqueous solution. The organic layer was dried with magnesium sulfate and the solvent was removed by rotary evaporation. The remaining residue was loaded onto a silica gel column and eluted with hexane.
Yield: 5.3 g (47 %).
Lithium! 1 -[2-methyl, 4-(2-methylphenyl)indenide] }
2-Methyl, 4-(2-methylphenyl)indene (5.3 g, 5.9 mmol) was dissolved in 100 mL of pentane. To this solution was added 9.6 mL of n-BuLi (2.5M in hexane) and the reaction was allowed to stir 5 hours at room temperature. A yellow-white solid precipitated from solution and was collected by frit filtration and washed with additional pentane. Yield: 4.6 g (87%).
Dimethylsilanediylbis! 1 -[2-methyl, 4-(2-methylphenyl)indene]}
Me2SiCl2 (1.3 g, 10 mmol) was dissolved in 80 mL of pentane and 60 ml of THF. While stirring, lithium{ l -[2-methyl, 4-(2-methylphenyl)-indenide]} (4.6 g, 20 mmol) was added as a dry powder and the contents were allowed to stir at reflux for 4 hours. The solvent was removed in vacuo and the residue was taken up in pentane and filtered to remove LiCl salts. The pentane was removed in vacuo, and the crude product was isolated as a viscous oil. Yield: 3.5 g (69 %).
Dilithium dimethylsilanediylbis! 1 -[2-methyl, 4-(2-methy lpheny l)indenide]} Dimethylsilanediylbis! l-[2-methyl, 4-(2-methylphenyl)indene]} (3.5 g, 4.8 mmol) was dissolved in 80 mL of Et O. To this solution was added 5.4 mL of n-BuLi (2.5M in hexane) and the reaction was allowed to stir for 3 hours. The solution was filtered through a celite-packed frit and the solvent was removed in vacuo to produce a flaky white solid, which was washed with pentane. Yield of solid: 3.0 g (86%). Dimefhylsilanediylbis! ! -[2-methyl, 4-(2 -methy lphenyl)indenyl] } zirconium dichloride
Dilithiumdimethylsilanediylbis! l-[2-methyl,4-(2-methylphenyl)indenide]}
(3.0g, 5.9 mmol) was dissolved in 80 mL of Et2O and cooled to -30 °C. To this solution was added ZrCl4 (1.37 g, 5.9 mmol) as a dry powder and the reaction was stirred at room temperature overnight. The solvent was removed in vacuo and the residue was taken up in toluene. The solution was filtered through a celite packed frit to remove LiCl, concentrated and cooled to -35 °C to induce crystallization.
Yellow-orange crystals of the racemic isomer were isolated. Yield: 220 mg (5.1%).
Supported Metallocene Catalyst System 4
In a 100 mL round bottom flask dimethylsilanediylbis{ l-[2-methyl,4-(2- methylphenyl)indenyl]} zirconium dichloride (0.058 g) was added to the above MAO-toluene solution (6.74 g, 7.35 mL) and stirred for twenty minutes. The resultant mixture was filtered through a medium glass frit funnel and washed with toluene (14 mL). To the combined filtrates was added dehydrated silica (4.0 g, Davison 948 Regular, 600°C dehydration). This slurry was stirred for twenty minutes, then dried at 40 °C for two minutes under vacuum on a rotary evaporator until the liquid evaporated and then the solid was further dried a total of about 2 hours and thirty two minutes. The supported catalyst was recovered as a salmon orange, free flowing solid (5.34 g).
EXAMPLE 5 2-Methyl, 4-(2-ethylphenyl)-indene
2-Ethylphenylbromide (10.0 g, 46 mmol) and magnesium turnings (2.0 g, 83 mmol) were taken up in 150 mL of Et2O and stirred at room temperature for 4 hours to form the Grignard solution. In a separate flask, NiCl (PPh3) (1.8 g, 2.8 mmol) and 4-chloro-2-methylindene (7.5 g, 46 mmol) were dissolved in 150 mL of Et2O. The Grignard solution was added dropwise to this solution and allowed to stir overnight at reflux. After overnight stirring, the reaction was slowly quenched with H2O to neutralize unreacted Grignard. Thereafter the solution was treated with 100 mL of 10% HCl(aq), and neutralized with saturated sodium bicarbonate aqueous solution. The organic layer was dried with magnesium sulfate and the solvent was removed by rotary evaporation. The remaining residue was loaded onto a silica gel column and eluted with hexane. Yield: 7.6 g (71 %).
Lithium! 1 -[2-methyl, 4-(2-ethylphenyl)indenide]}
2-Methyl, 4-(2-ethylphenyl)-indene (7.6 g, 32 mmol) was dissolved in 80 mL of pentane. To this solution was added 13 mL of n-BuLi (2.5M in hexane) and the reaction was allowed to stir 5 hours at room temperature. A yellow-white solid precipitated from solution and was collected by frit filtration and washed with additional pentane. Yield: 7.0 g (92%).
Dimethylsilanediylbis! 1 -[2-methyl, 4-(2-ethylphenyl)indene]} Me2SiCl2 (0.82 g, 6.4 mmol) was dissolved in 80 mL of pentane and 50 ml of THF. While stirring, lithium{ l-[2-methyl, 4-(2-ethylphenyl)indenide]} 0-0 g,
13 mmol) was added as a dry powder and the contents were allowed to stir at reflux overnight. The solvent was removed in vacuo and the residue was taken up in pentane and filtered to remove LiCl salts. The pentane was removed in vacuo, and the crude product was isolated as a fluffy white solid. Yield: 2.8 g (86%).
Dimethylsilanediylbis ! 1 -[2-methyl, 4-(2-ethylphenyl)indenyl] } zirconium dichloride
Dimethylsilanediylbis! 1 -[2-methyl, 4-(2-ethylphenyl)indene]} (2.5 g, 4.7 mmol) was dissolved in 50 mL of Et2O. To this solution was added 4.4 mL of n- BuLi (2.5M in hexane) and the solution was allowed to stir at room temperature for 2 hours. After this time, the solution was cooled to -35 °C and ZrCl4 (1.1 g,
4.7 mmol) was added as a dry powder. The reaction was allowed to warm to room temperature and was stirred overnight. The solution was filtered through a celite-packed frit to remove LiCl, concentrated, and cooled to -35 °C to induce crystallization. Yellow-orange crystals of the racemic isomer were obtained.
Yield: 170 mg (5.2%). Supported Metallocene Catalyst System 5
In a 100 mL round bottom flask dimethylsilanediylbis! l-[2-methyl, 4-(2- ethylphenyl)indenyl]} zirconium dichloride (0.061 g) was added to the above MAO-toluene solution (6.74 g) and stirred twenty minutes. The resultant mixture was filtered through a medium glass frit funnel and washed with toluene (14 mL).
To the combined filtrates was added dehydrated silica (4.0 g, Davison 948 Regular, 600°C dehydration). This slurry was stirred for twenty minutes, then dried at 40 °C for two minutes under vacuum on a rotary evaporator until the liquid evaporated and then the solid was further dried a total of about two hours and thirty three minutes. The supported catalyst was recovered as a pink, free flowing solid (5.57 g).
EXAMPLE 6
2-Methyl, 4-(2-isopropylphenyl)-indene 2-Isopropylbromobenzene (10 g, 45 mmol) and magnesium (2.4 g, 100 mmol) were combined in 200 mL of diethyl ether and stirred at room temperature overnight to form a Grignard solution. 4-Chloro-2-methylindene (7.4 g, 45 mmol) and NiCl2(PPh3)2 (1.8g, 2.8 mmol) were dissolved in 150 mL of Et2O. To this was added the Grignard solution and the reaction was stirred overnight at room temperature. After overnight stirring, the reaction was slowly quenched with H2O to neutralize unreacted Grignard. The solution was subsequently treated with 100 mL of 10% HCl(aq), and neutralized with saturated sodium bicarbonate aqueous solution. The organic layer was dried with magnesium sulfate and the solvent was removed by rotary evaporation. The remaining residue was loaded onto a silica gel column and eluted with hexane. Yield: 4.4 g (39%).
Lithium! 1 -[2-methyl, 4-(2-isopropylphenyl)indenide]}
2-Methyl, 4-(2-isopropylphenyl)-indene (4.4 g, 18 mmol) was dissolved in
80 mL of pentane. To this solution was added 7.0 mL of n-BuLi (2.5M in hexane) and the reaction was allowed to stir 4 hours at room temperature. A white solid precipitated from solution and was collected by frit filtration and washed with additional pentane. Yield: 4.0 g (90 %). Dimethy lsilanediylbis ! 1 - [2-methyl, 4-(2-isopropylphenyl)indene] } Me2SiCl2 (1.0 g, 7.7 mmol) was dissolved in 80 mL of THF. While stirring, lithium{l -[2-methyl, 4-(2-isopropylphenyl)indenide]} (4.0 g, 15.5 mmol) was added as a dry powder and the contents were allowed to stir overnight at room temperature. The solvent was removed in vacuo and the residue was taken up in pentane and filtered to remove LiCl salts. The pentane was removed in vacuo to yield a flaky white solid (2.1 g, 48 %).
Dimethylsilanediylbis! 1 -[2-methyl, 4-(2-isopropylphenyl)indenyl] } zirconium dichloride
Dimethylsilanediylbis! 1 -[2-methyl, 4-(2-isopropylphenyl)indene]} (2.1 g, 3.8 mmol) was dissolved in 60 mL of Et2O. While stirring, 3.0 mL of n-BuLi (2.5M in hexane) was added and allowed to stir at room temperature for 2 hours. After this time, the solution was cooled to -35 °C and ZrCl4 (0.88 g, 3.8 mmol) was added and allowed to stir at room temperature for 3 hours. The solvent was then removed in vacuo and the residue was taken up in a mixture of methylene chloride and pentane and filtered to remove LiCl salts. The filtrate was then concentrated and chilled to -35 °C to induce crystallization. 0.34 g (13%) of pure racemic compound was obtained.
Supported Metallocene Catalyst System 6 In a 100 mL round bottom flask dimethylsilanediylbis! 1 -[2-methyl, 4-(2- isopropylphenyl)indenyl]} zirconium dichloride (0.063 g) was added to the above MAO-toluene solution (6.74 g, 7.2 mL) and stirred twenty minutes. The resultant mixture was filtered through a medium glass frit funnel and washed with toluene
(14 mL). To the combined filtrates was added dehydrated silica (4.0 g, Davison 948 Regular, 600°C dehydration). This slurry was stirred for twenty minutes, then dried at 40 °C for two minutes under vacuum on a rotary evaporator until the liquid evaporated and then the solid was further dried a total of about two hours and twenty two minutes. The supported catalyst was recovered as a light orange, free flowing solid (5.56 g). EXAMPLE 7
2-Methyl, 4-(2-biphenylyl)-indene
Magnesium (2.0 g, 83 mmol), 2-bromobiphenyl (10 g, 43 mmol) were added together in 100 mL of diethyl ether and allowed to stir overnight at reflux to form a Grignard solution. 4-Chloro-2-methylindene (6.4 g, 43 mmol) and
NiCl2(PPh3)2 (1.5 g, 2.3 mmol) were dissolved in 150 mL of Et2O. The Grignard solution was added and the reaction was stirred overnight at reflux. After overnight stirring, the reaction was slowly quenched with H2O to neutralize unreacted Grignard. The solution was subsequently treated with 100 mL of 10% HCl(aq), and neutralized with saturated sodium bicarbonate aqueous solution.
The organic layer was dried with magnesium sulfate and the solvent was removed by rotary evaporation. The remaining residue was loaded onto a silica gel column and eluted with hexane. Yield: 3.9 g (32%).
Lithium ! 1 -[2-methyl, 4-(2-biphenylyl)indenide] }
2-Methyl, 4-(2-biphenylyl)-indene (3.9 g, 14 mmol) was dissolved in 100 mL of pentane. To this solution was added 5.6 mL of n-BuLi (2.5M in hexane) and the reaction was allowed to stir 4 hours at room temperature. A white solid precipitated from solution and was collected by frit filtration and washed with additional pentane. Yield: 3.0 g (76%).
Dimethylsilanediylbis! 1 -[2-methyl, 4-(2-biphenylyl)indene]} Me SiCl2 (0.67 g, 5.2 mmol) was dissolved in 60 mL of diethyl ether. While stirring, lithium! l-[2 -methyl, 4-(2-biphenylyl)indenide]} (3.0 g, 10 mmol) was added as a dry powder and a few drops of THF were added to catalyze the reaction. The contents were allowed to stir overnight at room temperature. The solvent was removed in vacuo and the residue was taken up in pentane and filtered to remove LiCl salts. The pentane was removed in vacuo to yield a flaky white solid. Yield: 2.3g (72%). Dimethylsilanediylbis! ! -[2-methyl, 4-(2-biρhenylyl)indenyl] } zirconium dichloride
Dimethylsilanediylbis! 1 -[2-methyl, 4-(2-biphenylyl)indene]} (2.3 g, 3.7 mmol) was dissolved in 50 mL of Et O. While stirring, 3.0 mL of n-BuLi (2.5M in hexane) was added and allowed to stir at room temperature for 0.5 hours. After this time, the solution was cooled to -35 °C and ZrCl (0.87 g, 3.7 mmol) was added and allowed to stir at room temperature for 3 hours. The solvent was then removed in vacuo and the residue was taken up in a mixture of methylene chloride and pentane and filtered to remove LiCl salts. The filtrate was then concentrated and chilled to -35 °C to induce crystallization. 0.22 g (7.5%) of pure racemic isomer was isolated.
Supported Metallocene Catalyst System 7
In a 100 mL round bottom flask dimethylsilanediylbis! 1 -[2-methyl, 4-(2- biphenylyl)indenyl]} zirconium dichloride (0.058 g) was added to the above
MAO-toluene solution (5.68 g, 6.05 mL) and stirred twenty minutes. The resultant mixture was filtered through a medium glass frit funnel and washed with toluene (11.8 mL). To the combined filtrates was added dehydrated silica (3.37 g, Davison 948 Regular, 600°C dehydration). This slurry was stirred for twenty minutes, then dried at 40 °C for two minutes under vacuum on a rotary evaporator until the liquid evaporated and then the solid was further dried a total of about 2 hours and twelve minutes. The supported catalyst was recovered as a pink-red, free flowing solid (4.58 g).
EXAMPLE 8
2-Methyl, 4-(4-biphenylyl)-indene 4-Bromobiphenyl (10 g, 39 mmol) and magnesium (2.0 g, 83 mmol) were combined in 100 mL of diethyl ether and stirred at room temperature overnight to form a Grignard solution. 4-Chloro-2-methylindene (6.4 g, 39 mmol) and NiCl2(PPh3)2 (1.8g, 2.8 mmol) were dissolved in 150 mL of Et2O. To this was added the Grignard solution and the reaction was stirred overnight at room temperature. After overnight stirring, the reaction was slowly quenched with H2O to neutralize unreacted Grignard. The solution was subsequently treated with 100 mL of 10% HCl(aq), and neutralized with saturated sodium bicarbonate aqueous solution. The organic layer was dried with magnesium sulfate and the solvent was removed by rotary evaporation. The remaining residue was loaded onto a silica gel column and eluted with hexane. Yield: 5.3 g (44%).
Lithium! 1 -[2-methyl, 4-(4-biphenylyl)indenide]}
2-Methyl, 4-(4-biphenylyl)-indene (5.3 g, 19 mmol) was dissolved in 80 mL of pentane. To this solution was added 7.5 mL of n-BuLi (2.5M in hexane) and the reaction was allowed to stir 4 hours at room temperature. A white solid precipitated from solution and was collected by frit filtration and washed with additional pentane. Yield: 3.4 g (64 %).
Dimethylsilanediylbis! l-[2-methyl, 4-(4-biphenylyl)indene]} Me2SiCl2 (0.77 g, 5.9 mmol) was dissolved in 80 mL of THF. While stirring, lithium! 1 -[2-methyl, 4-(4-biphenylyl)indenide]} (3.4 g, 12 mmol) was added as a dry powder and the contents were allowed to stir overnight at room temperature. The solvent was removed in vacuo and the residue was taken up in pentane and filtered to remove LiCl salts. The pentane was removed in vacuo to yield a flaky white solid (1.8 g, 49%).
Dimethylsilanediylbis! 1 -[2-methyl, 4-(4-biphenylyl)indenyl] } zirconium dichloride
Dimethylsilanediylbis! 1 -[2-methyl, 4-(4-biphenylyl)indene]} (1.8 g, 2.9 mmol) was dissolved in 60 mL of Et2O. While stirring, 2.3 mL of n-BuLi (2.5M in hexane) was added and allowed to stir at room temperature for 2 hours. After this time, the solution was cooled to -35 °C and ZrCl4 (0.67 g, 5.2 mmol) was added and allowed to stir at room temperature for 3 hours. The solvent was then removed in vacuo and the residue was taken up in a mixture of methylene chloride and pentane and filtered to remove LiCl salts. The filtrate was then concentrated and chilled to -35 °C to induce crystallization. 0.093 g (4.1%) of pure racemic compound was obtained. Supported Metallocene Catalyst System 8
In a 100 mL round bottom flask dimethylsilanediylbis! 1 -[2-methyl, 4-(4- biphenylyl)indenyl]} zirconium dichloride (0.075 g) was mixed with the above MAO-toluene solution (7.2 g, 7.8 mL) and stirred twenty minutes. The resultant mixture was filtered through a medium glass frit funnel and washed with toluene
(14 mL). To the combined filtrates was added dehydrated silica (4.0 g, Davison 948 Regular, 600°C dehydration). This slurry was stirred for twenty minutes, then dried at 40 °C for two minutes under vacuum on a rotary evaporator until the liquid evaporated and then the solid was further dried a total of about 2 hours and twenty seven minutes. The supported catalyst was recovered as a reddish pink, free flowing solid (5.25 g).
EXAMPLE 9
2-Methyl, 4-(4-tert-butylphenyl)-indene Magnesium (3.4 g, 141 mmol) and 4-tert-butylbromobenzene (20 g, 94 mmol) were added together in 200 mL of diethyl ether and allowed to stir overnight at reflux to form a Grignard solution. 4-Chloro-2-methylindene (15.4 g,
94 mmol) and NiCl2(PPh3)2 (1.5 g, 2.3 mmol) were dissolved in 200 mL of Et2O.
The Grignard solution was added and the reaction was stirred overnight at reflux. After overnight stirring, the reaction was slowly quenched with H2O to neutralize unreacted Grignard. The solution was subsequently treated with 100 mL of 10% HCl(aq), and neutralized with saturated sodium bicarbonate aqueous solution. The organic layer was dried with magnesium sulfate and the solvent was removed by rotary evaporation. The remaining residue was loaded onto a silica gel column and eluted with hexane. Yield: 9.8 g (40%).
Lithium! 1 -[2-methyl, 4-(4-tert-buty lpheny Qindenide]}
2-Methyl, 4-(4-tert-butylphenyl)-indene (4.0 g, 15 mmol) was dissolved in
100 mL of pentane. To this solution was added 6.1 mL of n-BuLi (2.5M in hexane) and the reaction was allowed to stir 4 hours at room temperature. A white solid precipitated from solution and was collected by frit filtration and washed with additional pentane. Yield: 4.0 g (99%). Dimethylsilanediylbis! 1 -[2-methyl, 4-(4-tert-butylphenyl)indene]} Me2SiCl2 (0.98 g, 7.6 mmol) was dissolved in 50 mL of diethyl ether. While stirring, lithium{ l -[2-methyl, 4-(4-tert-butylphenyl)indenide]} (4.0 g, 15 mmol) was added as a dry powder and a few drops of THF were added to catalyze the reaction. The contents were allowed to stir overnight at room temperature.
The solvent was removed in vacuo and the residue was taken up in pentane and filtered to remove LiCl salts. The pentane was removed in vacuo to yield an oil. The crude oil was loaded onto a silica gel column and eluted with hexane. Yield of product was 2.4 g (54%).
Dimethylsilanediylbis! ! -[2-methyl, 4-(4-tert-butylphenyl)indenyl]} zirconium dichloride
Dimethylsilanediylbis! ! -[2-methyl, 4-(4-tert-butylphenyl)indene]} (2.4 g,
4.1 mmol) was dissolved in 40 mL of Et2O. While stirring, 5.6 mL of n-BuLi (2.5M in hexane) was added and allowed to stir at room temperature for 0.5 hours.
After this time, the solution was cooled to -35 °C and ZrCl (0.96 g, 4.1 mmol) was added and allowed to stir at room temperature for 3 hours. The solvent was then removed in vacuo and the residue was taken up in a mixture of methylene chloride and pentane and filtered to remove LiCl salts. The filtrate was then concentrated and chilled to -35 °C to induce crystallization. Yield of product was
1.4 g (46%) as 1 : 1 mixture of racemic and meso isomers.
Supported Metallocene Catalyst System 9
In a 100 mL round bottom flask a racemic/meso mixture of dimethylsilanediylbis! 1 - [2-methyl,4-(4-tert-buty lpheny l)indenyl]} zirconium dichloride (0.030 g) was added to the above MAO-toluene solution (3.37 g, 3.6 mL) and stirred twenty minutes. The resultant mixture was filtered through a medium glass frit funnel and washed with toluene (7 mL). To the combined filtrates was added dehydrated silica (2.0 g, Davison 948 Regular, 600°C dehydration). This slurry was stirred for twenty minutes, then dried at 40 °C for two minutes under vacuum on a rotary evaporator until the liquid evaporated and then the solid was further dried a total of about 2 hours and fifteen minutes. The supported catalyst was recovered as a pinkish, free flowing solid ( 2.55 g).
EXAMPLE 10 2-Methyl, 4-(2,3-dimethylphenyl)-indene
3-Bromo-o-xylene (12.0 g, 64 mmol) and magnesium turnings (2.3 g, 96 mmol) were taken up in 200 mL of Et2O and stirred at room temperature overnight to form a Grignard solution. In a separate flask, NiCl2(PPh )2 (1.8 g, 2.8 mmol) and 4-chloro-2-methylindene (1 1 g, 64 mmol) were dissolved in 100 mL of Et2O. The Grignard solution was added dropwise to this solution and allowed to stir overnight at reflux. After overnight stirring, the reaction was slowly quenched with H2O to neutralize unreacted Grignard. The solution was subsequently treated with 100 mL of 10% HCl(aq), and neutralized with saturated sodium bicarbonate aqueous solution. The organic layer was dried with magnesium sulfate and the solvent was removed by rotary evaporation. The remaining residue was loaded onto a silica gel column and eluted with hexane. Yield: 6.6 g (44 %).
Lithium! 1 -[2-methyl, 4-(2,3-dimethylphenyl)indenide]}
2-Methyl, 4-(2,3-dimethylphenyl)-indene (6.6 g, 28 mmol) was dissolved in 200 mL of pentane. To this solution was added 11 mL of n-BuLi (2.5M in hexane) and 3 mL of diethyl ether and the reaction was allowed to stir 1 hour at room temperature. A yellow-white solid precipitated from solution and was collected by frit filtration and washed with additional pentane. Yield: 6.5 g (99%).
Dimethylsilanediylbis! 1 -[2-methyl, 4-(2,3-dimethylphenyl)indene]}
Me2SiCl2 (0.81 g, 6.3 mmol) was dissolved in 40 ml of THF. While stirring, lithium {1 -[2-methyl, 4-(2,3-dimethylphenyl)indenide]} (3.0 g, 13 mmol) was added as a dry powder and the contents were allowed to stir at reflux overnight. The solvent was removed in vacuo and the residue was taken up in pentane and filtered to remove LiCl salts. The pentane solution was cooled and white crystals of the product precipitated from solution. Yield: 3.3 g (100%). Dimethylsilanediylbis! l-[2-methyl, 4-(2,3-dimethylphenyl)indenyl]}zirconium dichloride
Dimethylsilanediylbis! 1 -[2-methyl, 4-(2,3-dimethylphenyl)indene]} (3.3 g, 6.3 mmol) was dissolved in 50 mL of Et2O. To this solution was added 5.0 mL of n-BuLi (2.5M in hexane) and stirred for 3 hours. The solution was then cooled to -30 °C and ZrCl4 (1.5 g, 6.3 mmol) was added as a dry powder and the reaction was stirred at room temperature overnight. The solvent was removed in vacuo and the residue was taken up in toluene. The solution was filtered through a celite packed frit to remove LiCl, concentrated and cooled to -35C to induce crystallization. Yellow-orange crystals of the racemic isomer were isolated.
Yield: 220 mg (5.1%).
Supported Metallocene Catalyst System 10
In a 100 mL round bottom flask dimethylsilanediylbis { 1 -[2-methyl, 4- (2,3-dimethylphenyl)indenyl]}zirconium dichloride (0.061 g) was added to the above MAO-toluene solution (6.74 g, 7.2 mL) and stirred twenty minutes. The resultant mixture was filtered through a medium glass frit funnel and washed with toluene (14 mL). To the combined filtrates was added dehydrated silica (4.0 g, Davison 948 Regular, 600°C dehydration). This slurry was stirred for twenty minutes, then dried at 40 °C for two minutes under vacuum on a rotary evaporator until the liquid evaporated and then the solid was further dried a total of about 2 hours and thirty minutes. The supported catalyst was recovered as a pink, free flowing solid (5.53 g).
EXAMPLE 11
2-Methyl, 4-(2,4-dimethylphenyl)-indene 4-Bromo-m-xylene (15 g, 80 mmol) and magnesium turnings (2.9 g, 120 mmol) were taken up in 200 mL of diethyl ether and stirred at room temperature overnight to form a Grignard solution. In a separate flask, NiCl2(PPh3)2 (1.8 g, 2.8 mmol) and 4-chloro-2-methylindene (13 g, 80 mmol) were dissolved in 100 mL of
Et2O. The Grignard solution was added dropwise to this solution and allowed to stir overnight at reflux. After overnight stirring, the reaction was slowly quenched with H O to neutralize unreacted Grignard. The solution was subsequently treated with 100 mL of 10% HCl(aq), and neutralized with saturated sodium bicarbonate aqueous solution. The organic layer was dried with magnesium sulfate and the solvent was removed by rotary evaporation. The remaining residue was loaded onto a silica gel column and eluted with hexane. Yield: 11 g (59 %).
Lithium! 1 -[2-methyl, 4-(2,4-dimethylphenyl)indenide]}
2-Methyl, 4-(2,4-dimethylphenyl)-indene (1 1 g, 28 mmol) was dissolved in 200 mL of pentane. To this solution was added 19 mL of n-BuLi (2.5M in hexane) and 3 mL of diethyl ether and the reaction was allowed to stir 1 hour at room temperature. A yellow-white solid precipitated from solution and was collected by frit filtration and washed with additional pentane. Yield: 11 g (99%).
Dimethylsilanediylbis! 1 -[2-methyl, 4-(2,4-dimethylphenyl)indene] } Me2SiCl2 (0.83 g, 6.4 mmol) was dissolved in 40 ml of THF. While stirring, lithium{ l -[2-methyl, 4-(2,4-dimethylphenyl)indenide]} (3.0 g, 13 mmol) was added as a dry powder and the contents were allowed to stir at reflux overnight. The solvent was removed in vacuo and the residue was taken up in pentane and filtered to remove LiCl salts. The pentane solution was cooled and white crystals of the product precipitated from solution. Yield: 3.3 g (100%).
Dimethylsilanediylbis! l-[2-methyl, 4-(2,4-dimethylphenyl)indenyl]} zirconium dichloride
Dimethylsilanediylbis! 1 -[2-methyl, 4-(2,4-dimethylphenyl)indene]} (3.3 g, 6.3 mmol) was dissolved in 50 mL of Et2O. To this solution was added 5.0 mL of n-BuLi (2.5M in hexane) and stirred for 3 hours. The solution was then cooled to -30 °C and ZrCl4 (1.5 g, 6.3 mmol) was added as a dry powder and the reaction was stirred at room temperature overnight. The solvent was removed in vacuo and the residue was taken up in toluene. The solution was filtered through a celite packed frit to remove LiCl, concentrated and cooled to -35 °C to induce crystallization. Yellow-orange crystals of the racemic isomer were isolated.
Yield: 700 mg (16%). Supported Metallocene Catalyst System 11
In a 100 mL round bottom flask dimethylsilanediylbis! 1 -[2-methyl, 4- (2,4-dimethylphenyl)indenyl]} zirconium dichloride (0.061 g) was added to the above MAO-toluene solution (6.74 g, 7.2 mL) and stirred twenty minutes. The resultant mixture was filtered through a medium glass frit funnel and washed with toluene (14 mL). To the combined filtrates was added dehydrated silica (4.0 g, Davison 948 Regular, 600°C dehydration). This slurry was stirred for twenty minutes, then dried at 40 °C for two minutes under vacuum on a rotary evaporator until the liquid evaporated and then the solid was further dried a total of about two hours and fifteen minutes. The supported catalyst was recovered as a pinkish red, free flowing solid (5.68 g).
EXAMPLE 12
2-Methyl, 4-(2,6-dimethylphenyl)-indene 2-Bromo-m-xylene (10.0 g, 54 mmol) and magnesium turnings (2.4 g, 100 mmol) were taken up in 150 mL of Et O and stirred at room temperature for 4 hours to form a Grignard solution. In a separate flask, NiCl2(PPh3)2 (1.8 g, 2.8 mmol) and 4-chloro-2-methylindene (8.9 g, 54 mmol) were dissolved in 150 mL of Et2O. The Grignard solution was added dropwise to this solution and allowed to stir overnight at reflux. After overnight stirring, the reaction was slowly quenched with H O to neutralize unreacted Grignard. The solution was subsequently treated with 100 mL of 10% HCl(aq), and neutralized with saturated sodium bicarbonate aqueous solution. The organic layer was dried with magnesium sulfate and the solvent was removed by rotary evaporation. The remaining residue was loaded onto a silica gel column and eluted with hexane.
Yield: 4.0 g (32 %).
Lithium! 1 -[2-methyl, 4-(2,6-dimethylphenyl)indenide]} 2-Methyl, 4-(2,6-dimethylphenyl)-indene (4.0 g, 17 mmol) was dissolved in 80 mL of pentane. To this solution was added 6.8 mL of n-BuLi (2.5M in hexane) and the reaction was allowed to stir 2 hours at room temperature. A yellow-white solid precipitated from solution and was collected by frit filtration and washed with additional pentane. Yield: 4.0 g (100%).
Dimethylsilanediylbis! 1 -[2-methyl, 4-(2,6-dimethylphenyl)indene]} Me SiCl2 (1.1 g, 8.5 mmol) was dissolved in 80 ml of THF. While stirring, lithium{ l-[2-methyl, 4-(2,6-dimethylphenyl)indenide]} (4.0 g, 17 mmol) was added as a dry powder and the contents were allowed to stir at reflux overnight. The solvent was removed in vacuo and the residue was taken up in pentane and filtered to remove LiCl salts. The pentane solution was cooled and white crystals of the product precipitated from solution. Yield: 1.7 g (86%).
Dimethylsilanediylbis! 1 -[2 -methyl, 4-(2,6-dimethylphenyl)indenyl]} zirconium dichloride
Dimethylsilanediylbis! 1 -[2-methyl, 4-(2,6-dimethylphenyl)indene]} (1.4 g, 2.7 mmol) was dissolved in 80 mL of Et2O. To this solution was added 2.2 mL of n-BuLi (2.5M in hexane) and the solution was allowed to stir at room temperature for 2 hours. After this time, the solution was cooled to -35 °C and
ZrCl (0.63 g, 2.7 mmol) was added as a dry powder. The reaction was allowed to warm to room temperature and was stirred overnight. The solution was filtered through a celite-packed frit to remove LiCl, concentrated, and cooled to -35 °C to induce crystallization. Yellow-orange crystals of the racemic isomer were obtained. Yield: 450 mg (24%).
Supported Metallocene Catalyst System 12 In a 100 mL round bottom flask dimethylsilanediylbis! 1 -[2-methyl, 4-
(2,6-dimethylphenyl)indenyl]} zirconium dichloride (0.061 g) was added to the above MAO-toluene solution (6.74 g, 7.3 mL) and stirred twenty minutes. The resultant mixture was filtered through a medium glass frit funnel and washed with toluene (14 mL). To the combined filtrates was added dehydrated silica (4.0 g, Davison 948 Regular, 600°C dehydration). This slurry was stirred for twenty minutes, then dried at 40 °C for two minutes under vacuum on a rotary evaporator until the liquid evaporated and then the solid was further dried a total of about two hours and forty one minutes. The supported catalyst was recovered as a reddish orange, free flowing solid (5.39 g).
EXAMPLE 13 2-Methy 1 , 4-(2 , 5 -dimethy lpheny l)-indene
2-Bromo-p-xylene (20 g, 108 mmol) and magnesium turnings (4.0 g, 162 mmol) were taken up in 300 mL of Et2O and stirred at room temperature overnight to form a Grignard solution. In a separate flask, NiCl2(PPh3)2 (1.8 g, 2.8 mmol) and 4-chloro-2-methylindene (18 g, 108 mmol) were dissolved in 200 mL of Et2O. The Grignard solution was added dropwise to this solution and allowed to stir overnight at reflux. After overnight stirring, the reaction was slowly quenched with H2O to neutralize unreacted Grignard. The solution was subsequently treated with 100 mL of 10% HCl(aq), and neutralized with saturated sodium bicarbonate aqueous solution.The organic layer was dried with magnesium sulfate and the solvent was removed by rotary evaporation. The remaining residue was loaded onto a silica gel column and eluted with hexane. Yield: 9.2 g (36 %).
Dimethylsilanediylbis! 1 -[2-methyl, 4-(2,5-dimethy.phenyl)indene] } 2-Methyl, 4-(2,5-dimethylphenyl)-indene (4.0 g, 17 mmol) was dissolved in 30 mL of Et2O and cooled to -30°C. To this solution was added 6.8 mL of n- BuLi (2.5M in hexane) and the reaction was allowed to stir 1 hour at room temperature. Me2SiCl (1.1 g, 8.5 mmol) was dissolved in 20 ml of THF and added dropwise to the reaction and the contents were allowed to stir at reflux overnight. The solvent was removed in vacuo and the residue was taken up in pentane and filtered to remove LiCl salts. The pentane was removed in vacuo and the remaining residue was loaded onto a silica gel column and eluted with hexane. Yield of product was 2.8g (62%). Dimethylsilanediylbis! ! -[2-methyl, 4-(2,5-dimethylphenyl)indenyl]} zirconium dichloride
Dimethylsilanediylbis! 1 -[2-methyl, 4-(2,5-dimethylphenyl)indene]} (2.8 g, 5.3 mmol) was dissolved in 50 mL of Et O. To this solution was added 4.3 mL of n-BuLi (2.5M in hexane) and stirred for 3 hours. The solution was then cooled to -30 °C and ZrCl4 (1.2 g, 5.3 mmol) was added as a dry powder and the reaction was stirred at room temperature overnight. The solvent was removed in vacuo and the residue was taken up in toluene. The solution was filtered through a celite packed frit to remove LiCl, and concentrated and cooled to -35 °C to induce crystallization. Yellow-orange crystals of the racemic isomer were isolated. Yield:
60 mg (1.6%).
Supported Metallocene Catalyst System 13
In a 100 mL round bottom flask dimethylsilanediylbis! 1 -[2-methyl, 4- (2,5-dimethylphenyl)indenyl]} zirconium dichloride (0.061 g) was added to the above MAO-toluene solution (6.74 g, 7.3 mL) and stirred twenty minutes. The resultant mixture was filtered through a medium glass frit funnel and washed with toluene (14 mL). To the combined filtrates was added dehydrated silica (4.0 g, Davison 948 Regular, 600°C dehydration). This slurry was stirred for twenty minutes, then dried at 40 °C for two minutes under vacuum on a rotary evaporator until the liquid evaporated and then the solid was further dried a total of about two hours and thirty three minutes. The supported catalyst was recovered as a reddish pink, free flowing solid (5.48 g).
EXAMPLE 14
2-Methyl, 4-(2,3,4-trimethylphenyl)-indene 2,3,4-Trimethylbromobenzene (10 g, 50 mmol) and magnesium turnings (2.4 g, 100 mmol) were taken up in 150 mL of Et2O and stirred at room temperature overnight to form a Grignard solution. In a separate flask, NiCl2(PPh3)2 (1.8 g, 2.8 mmol) and 4-chloro-2-methylindene (8.3 g, 50 mmol) were dissolved in 200 mL of Et2O. The Grignard solution was added dropwise to this solution and allowed to stir overnight at reflux. After overnight stirring, the reaction was slowly quenched with H2O to neutralize unreacted Grignard. The solution was subsequently treated with 100 mL of 10% HCl(aq), and neutralized with saturated sodium bicarbonate aqueous solution. The organic layer was dried with magnesium sulfate and the solvent was removed by rotary evaporation. The remaining residue was loaded onto a silica gel column and eluted with hexane.
Yield: 5.5 g (44 %).
Lithium! 1 -[2-methyl, 4-(2,3, 4-trimethy lphenyl)indenide]} 2-Methyl, 4-(2,3,4-trimethylphenyl)-indene (5.5 g, 22 mmol) was dissolved in 200 mL of pentane. To this solution was added 8.9 mL of n-BuLi
(2.5M in hexane) and 3 mL of diethyl ether and the reaction was allowed to stir 1 hour at room temperature. A yellow-white solid precipitated from solution and was collected by frit filtration and washed with additional pentane. Yield: 5.3 g (97%).
Dimethylsilanediylbis! ! -[2-methyl, 4-(2,3,4-trimethylphenyl)indene]} Me2SiCl2 (0.76 g, 5.9 mmol) was dissolved in 40 ml of THF. While stirring, lithium {1 -[2-methyl, 4-(2,3,4-trimethylphenyl)indenide]} (3.0 g, 12 mmol) was added as a dry powder and the contents were allowed to stir at reflux overnight. The solvent was removed in vacuo and the residue was taken up in pentane and filtered to remove LiCl salts. The pentane was removed in vacuo, and the crude product was isolated. Yield: 3.5 g (100 %).
Dimethylsilanediylbis ! 1 -[2-methyl, 4-(2,3 ,4-trimethy lphenyl)indenyl] } zirconium dichloride
Dimethylsilanediylbis! l-[2-methyl, 4-(2, 3, 4-trimethy lphenyl)indene] } (3.5 g, 5.9 mmol) was dissolved in 50 mL of Et2O. To this solution was added 9.4 mL of n-BuLi (2.5M in hexane) and stirred for 1 hour. The solution was then cooled to -30 °C and ZrCl4 (1.4 g, 5.9 mmol) was added as a dry powder and the reaction was stirred at room temperature overnight. The solvent was removed in vacuo and the residue was taken up in toluene. The solution was filtered through a celite packed frit to remove LiCl, concentrated and cooled to -35 °C to induce crystallization. Yellow-orange crystals of the racemic isomer were isolated. Yield: 350 mg (8.0%).
Supported Metallocene Catalyst System 14 In a 100 mL round bottom flask dimethylsilanediylbis! 1 -[2-methyl, 4-
(2,3, 4-trimethylphenyl)indenyl]} zirconium dichloride (0.063 g) was added to the above MAO-toluene solution (6.74 g, 7.2 mL) and stirred twenty minutes. The resultant mixture was filtered through a medium glass frit funnel and washed with toluene (14 mL). To the combined filtrates was added dehydrated silica (4.0 g, Davison 948 Regular, 600°C dehydration). This slurry was stirred for twenty minutes, then dried at 40 °C for two minutes under vacuum on a rotary evaporator until the liquid evaporated and then the solid was further dried a total of about two hours and twenty minutes. The supported catalyst was recovered as an orange, free flowing solid (5.29 g).
EXAMPLE 15
2-Methyl, 4-(2,4,5-trimethylphenyl)-indene 2,4,5-Trimethylbromobenzene (10 g, 50 mmol) and magnesium (2.4 g, 100 mmol) were combined in 200 mL of diethyl ether and stirred at room temperature overnight to form a Grignard solution. 4-Chloro-2-methylindene (8.3 g, 50 mmol) and NiCl2(PPh3)2 (1.8g, 2.8 mmol) were dissolved in 150 mL of Et2O. To this was added the Grignard solution and the reaction was stirred overnight at room temperature. After overnight stirring, the reaction was slowly quenched with H2O to neutralize unreacted Grignard. The solution was subsequently treated with 100 mL of 10% HCl(aq), and neutralized with saturated sodium bicarbonate aqueous solution. The organic layer was dried with magnesium sulfate and the solvent was removed by rotary evaporation. The remaining residue was loaded onto a silica gel column and eluted with hexane. Yield: 6.0 g (48%).
Lithium! 1 -[2-methyl, 4-(2,4,5-trimethylphenyl)indenide]}
2-Methyl, 4-(2,4,5-trimethylphenyl)-indene (6.0 g, 24 mmol) was dissolved in 80 mL of pentane. To this solution was added 9.7 mL of n-BuLi (2.5M in hexane) and the reaction was allowed to stir 4 hours at room temperature. A white solid precipitated from solution and was collected by frit filtration and washed with additional pentane. Yield: 5.5 g (92 %).
Dimethylsilanediylbis! 1 -[2-methyl, 4-(2,4,5-trimethylphenyl)indene]}
Me SiCl2 (0.76 g, 5.9 mmol) was dissolved in 80 mL of THF. While stirring, lithium! 1 -[2-methyl, 4-(2,4,5-trimethylphenyl)indenide]} (3.0 g, 12 mmol) was added as a dry powder and the contents were allowed to stir overnight at room temperature. The solvent was removed in vacuo and the residue was taken up in pentane and filtered to remove LiCl salts. The pentane was removed in vacuo to yield a flaky white solid (2.9 g, 88 %).
Dimethylsilanediylbis! ! -[2-methyl, 4-(2,4,5-trimethylphenyl)indenyl]}zirconium dichloride Dimethylsilanediylbis {1 -[2-methyl, 4-(2,4,5-trimethylphenyl)indene]} (2.9 g, 5.2 mmol) was dissolved in 60 mL of Et2O. While stirring, 4.1 mL of n-BuLi (2.5M in hexane) was added and allowed to stir at room temperature for 2 hours. After this time, the solution was cooled to -35 °C and ZrCl4 (1.2 g, 5.2 mmol) was added and allowed to stir at room temperature for 3 hours. The solvent was then removed in vacuo and the residue was taken up in a mixture of methylene chloride and pentane and filtered to remove LiCl salts. The filtrate was then concentrated and chilled to -35 °C to induce crystallization. 0.52 g (14%) of pure racemic compound was obtained.
Supported Metallocene Catalyst System 15
In a 100 mL round bottom flask dimethylsilanediylbis! 1 -[2-methyl, 4- (2,4,5-trimethylphenyl)indenyl]} zirconium dichloride (0.063 g) was added to the above MAO-toluene solution (6.74 g, 7.3 mL) and stirred twenty minutes. The resultant mixture was filtered through a medium glass frit funnel and washed with toluene (14 mL). To the combined filtrates was added dehydrated silica (4.0 g,
Davison 948 Regular, 600°C dehydration). This slurry was stirred for twenty minutes, then dried at 40 °C for two minutes under vacuum on a rotary evaporator until the liquid evaporated and then the solid was further dried a total of about two hours and thirty minutes. The supported catalyst was recovered as an orangish, free flowing solid (5.54 g).
EXAMPLE 16
2-Methyl, 4-(2,3,5,6-tetramethylphenyl)-indene 2,3,5,6-Tetramethylbromobenzene (10 g, 47 mmol) and magnesium (2.4 g, 100 mmol) were combined in 200 mL of diethyl ether and stirred at room temperature overnight to form a Grignard solution. 4-Chloro-2-mefhylindene (7.7 g, 47 mmol) and NiCl2(PPh3)2 (1.8g, 2.8 mmol) were dissolved in 150 mL of
Et2O. To this was added the Grignard solution and the reaction was stirred overnight at room temperature. After overnight stirring, the reaction was slowly quenched with H2O to neutralize unreacted Grignard. The solution was subsequently treated with 100 mL of 10% HCl(aq), and neutralized with saturated sodium bicarbonate aqueous solution. The organic layer was dried with magnesium sulfate and the solvent was removed by rotary evaporation. The remaining residue was loaded onto a silica gel column and eluted with hexane. Yield: 8.4 g (68%).
Lithium! 1 -[2-methyl, 4-(2,3,5,6-tetramethylphenyl)indenide]}
2-Methyl, 4-(2,3,5,6-tetramethylphenyl)-indene (8.4 g, 32 mmol) was dissolved in 80 mL of pentane. To this solution was added 13 mL of n-BuLi (2.5M in hexane) and the reaction was allowed to stir 4 hours at room temperature. A white solid precipitated from solution and was collected by frit filtration and washed with additional pentane. Yield: 8.0 g (95 %).
Dimethylsilanediylbis! l-[2 -methyl, 4-(2,3,5,6-tetramethylphenyl)indene]}
Me2SiCl2 (0.72 g, 5.5 mmol) was dissolved in 80 mL of THF. While stirring, lithium! 1 -[2-methyl, 4-(2,3,5,6-tetramethylphenyl)indenide]} (3.0 g, 11 mmol) was added as a dry powder and the contents were allowed to stir overnight at room temperature. The solvent was removed in vacuo and the residue was taken up in pentane and filtered to remove LiCl salts. The pentane was removed in vacuo to yield a flaky white solid (2.6 g, 81 %).
Dimethylsilanediylbis! 1 -[2-methyl, 4-(2,3,5,6-tetramethylphenyl)indenyl] } zirconium dichloride
Dimethylsilanediylbis! l-[2 -methyl, 4-(2,3,5,6-tetramethylphenyl)indene]} (2.6 g, 4.4 mmol) was dissolved in 60 mL of Et2O. While stirring, 3.8 mL of n- BuLi (2.5M in hexane) was added and allowed to stir at room temperature for 2 hours. After this time, the solution was cooled to -35 °C and ZrCl (1.0 g, 4.4 mmol) was added and allowed to stir at room temperature for 3 hours. The solvent was then removed in vacuo and the residue was taken up in a mixture of methylene chloride and pentane and filtered to remove LiCl salts. The filtrate was then concentrated and chilled to -35 °C to induce crystallization. 0.71 g (22%) of pure racemic compound was obtained.
Supported Metallocene Catalyst System 16
In a 100 mL round bottom flask dimethylsilanediylbis! 1 -[2-methyl, 4-
(2,3,5,6-tetramethylphenyl)indenyl]}zirconium dichloride ( 0.66 g) was added to the above MAO-toluene solution (6.74 g, 7.3 mL) and stirred twenty minutes. The resultant mixture was filtered through a medium glass frit funnel and washed with toluene (14 mL). To the combined filtrates was added dehydrated silica (4.0 g, Davison 948 Regular, 600°C dehydration). This slurry was stirred for twenty minutes, then dried at 40 °C for two minutes under vacuum on a rotary evaporator until the liquid evaporated and then the solid was further dried a total of about two hours and twenty minutes. The supported catalyst was recovered as a reddish pink, free flowing solid (5.77 g).
EXAMPLE 17
2-Isoproρyl, 4-(3-biphenylyl)-indene Magnesium (3.0 g, 125 mmol) and 3-bromobiphenyl (15 g, 65 mmol) were added together in 100 mL of diethyl ether and allowed to stir overnight at reflux to form a Grignard solution. 4-Chloro-2-isopropylindene (12.4 g, 65 mmol) and NiCl2(PPh3)2 (1.5 g, 2.3 mmol) were dissolved in 150 mL of Et2O. The Grignard solution formed was added and the reaction was stirred overnight at reflux. After overnight stirring, the reaction was slowly quenched with H O to neutralize unreacted Grignard. The solution was subsequently treated with 100 mL of 10% HCl(aq), and neutralized with saturated sodium bicarbonate aqueous solution.
The organic layer was dried with magnesium sulfate and the solvent was removed by rotary evaporation. The remaining residue was loaded onto a silica gel column and eluted with hexane. Yield: 8.9 g (45%).
Lithium! 1 -[2-isopropyl, 4-(3-biphenylyl)indenide]}
2-Isopropyl, 4-(3-biphenylyl)-indene (8.9 g, 29 mmol) was dissolved in 150 mL of pentane. To this solution was added 11.5 mL of n-BuLi (2.5M in hexane) and the reaction was allowed to stir 4 hours at room temperature. A white solid precipitated from solution and was collected by frit filtration and washed with additional pentane. Yield: 7.5 g (84%).
Dimethylsilanediylbis! 1 -[2-isopropyl, 4-(3-biphenylyl)indene]} Me SiCl2 (0.62 g, 4.8 mmol) was dissolved in 60 mL of diethyl ether. While stirring, lithium{ l -[2-isopropyl, 4-(3-biphenylyl)indenide]} (3.0 g, 9.5 mmol) was added as a dry powder and a few drops of THF was added to catalyze the reaction. The contents were allowed to stir overnight at room temperature. The solvent was removed in vacuo and the residue was taken up in pentane and filtered to remove LiCl salts. The pentane was removed in vacuo to yield a flaky white solid. Yield: 3.2g (100%).
Dimethylsilanediylbis!! -[2-isopropyl, 4-(3-biphenylyl)indenyl]} zirconium dichloride
Dimethylsilanediylbis! 1 -[2-isopropyl, 4-(3-biphenylyl)indene]} (3.2 g, 4.7 mmol) was dissolved in 50 mL of Et2O. While stirring, 3.8 mL of n-BuLi (2.5M in hexane) was added and allowed to stir at room temperature for 0.5 hours. After this time, the solution was cooled to -35 °C and ZrCl (1.1 g, 4.7 mmol) was added and allowed to stir at room temperature for 3 hours. The solvent was then removed in vacuo and the residue was taken up in a mixture of methylene chloride and pentane and filtered to remove LiCl salts. The filtrate was then concentrated and chilled to -35 °C to induce crystallization. 1.2 g (30%) of pure racemic isomer was isolated.
Supported Metallocene Catalyst System 17 In a 100 mL round bottom flask dimethylsilanediylbis! 1 -[2-isopropyl, 4- (3 -biphenylyl)indenyl] } zirconium dichloride (0.070 g) was added to the above MAO-toluene solution (6.74 g, 7.3 mL) and stirred twenty minutes. The resultant mixture was filtered through a medium glass frit funnel and washed with toluene
(14 mL). To the combined filtrates was added dehydrated silica (4.0 g, Davison 948 Regular, 600°C dehydration). This slurry was stirred for twenty minutes, then dried at 40 °C for two minutes under vacuum on a rotary evaporator until the liquid evaporated and then the solid was further dried a total of about two hours and twenty seven minutes. The supported catalyst was recovered as a light purple, free flowing solid (5.46 g).
EXAMPLE 18
2-Isopropyl, 4-(2-methylphenyl)-indene 4-Chloro-2-isopropylindene (9.8 g, 51 mmol) and NiCl2(PPh3)2 (1.8g, 2.8 mmol) were dissolved in 150 mL of Et O. 2-Methylphenylmagnesium bromide (51 mmol) as a Et2O solution was added to the solution and the reaction was stirred overnight at room temperature. After overnight stirring, the reaction was slowly quenched with H O to neutralize unreacted Grignard. he solution was subsequently treated with 100 mL of 10% HCl(aq), and neutralized with saturated sodium bicarbonate aqueous solution. The organic layer was dried with magnesium sulfate and the solvent was removed by rotary evaporation. The remaining residue was loaded onto a silica gel column and eluted with hexane. Yield: 6.6 g (52%). Lithium! 1 -[2-isopropyl, 4-(2-methylphenyl)indenide] }
2-Isopropyl, 4-(2-methylphenyl)-indene (6.6 g, 26.5 mmol) was dissolved in 80 mL of pentane. To this solution was added 10.6 mL of n-BuLi (2.5M in hexane) and the reaction was allowed to stir 4 hours at room temperature. A white solid precipitated from solution and was collected by frit filtration and washed with additional pentane. Yield: 5.8 g (88%).
Dimethylsilanediylbis! 1 -[2-isopropyl, 4-(2 -methy lphenyl)indene]} Me2SiCl2 (0.88 g, 6.8 mmol) was dissolved in 60 mL of THF. While stirring, lithium{ l -[2-isopropyl, 4-(2-methylphenyl)indenide]} (3.5 g, 13.7 mmol) was added as a dry powder and the contents were allowed to stir overnight at room temperature. The solvent was removed in vacuo and the residue was taken up in pentane and filtered to remove LiCl salts. The pentane was removed in vacuo to yield a flaky white solid (3.0 g).
Dimethylsilanediylbis! 1 -[2-isopropyl, 4-(2-methylphenyl)indenyl]} zirconium dichloride
Dimethylsilanediylbis! 1 -[2-isopropyl, 4-(2-methylphenyl)indene]} (3.0 g,
5.4 mmol) was dissolved in 60 mL of Et2O. While stirring, 4.5 mL of n-BuLi (2.5M in hexane) was added and allowed to stir at room temperature for 2 hours.
After this time, the solution was cooled to -35 °C and ZrCl4 (1.25 g, 5.4 mmol) was added and allowed to stir at room temperature for 3 hours. The solvent was then removed in vacuo and the residue was taken up in a mixture of methylene chloride and pentane and filtered to remove LiCl salts. The filtrate was then concentrated and chilled to -35 °C to induce crystallization. 0.26 g (6.7%) of pure racemic compound was obtained.
Supported Metallocene Catalyst System 18
In a 100 mL round bottom flask dimethylsilanediylbis! 1 -[2-isopropyl, 4- (2-methylphenyl)indenyl]} zirconium dichloride (0.064 g) was added to the above
MAO-toluene solution (6.74 g, 7.15 mL) and stirred twenty minutes. The resultant mixture was filtered through a medium glass frit funnel and washed with toluene (14 mL). To the combined filtrates was added dehydrated silica (4.0 g, Davison 948 Regular, 600°C dehydration). This slurry was stirred for twenty minutes, then dried at 40 °C for two minutes under vacuum on a rotary evaporator until the liquid evaporated and then the solid was further dried a total of about two hours and seventeen minutes. The supported catalyst was recovered as a pink-purple, free flowing solid (5.36 g).
EXAMPLE 19
2-Isopropyl, 4-(2,3-dimethylphenyl)-indene 4-Chloro-2-isopropylindene (10.4 g, 54 mmol) and NiCl2(PPh3)2 (1.5 g,
2.3 mmol) were dissolved in 80 mL of Et2O. 2,3 -Dimethy lpheny lmagnesium bromide (54 mmol) as a Et O solution was added to the solution and the reaction was stirred overnight at room temperature. After overnight stirring, the reaction was slowly quenched with H2O to neutralize unreacted Grignard. The solution was subsequently treated with 100 mL of 10% HCl(aq), and neutralized with saturated sodium bicarbonate aqueous solution. The organic layer was dried with magnesium sulfate and the solvent was removed by rotary evaporation. The remaining residue was loaded onto a silica gel column and eluted with hexane. Yield: 5.3 g (37%).
Lithium! 1 -[2-isopropyl, 4-(2,3-dimethylphenyl)indenide]} 2-Isopropyl, 4-(2,3-dimethylphenyl)-indene (5.3 g, 20 mmol) was dissolved in 80 mL of pentane. To this solution was added 8.1 mL of n-BuLi (2.5M in hexane) and the reaction was allowed to stir 4 hours at room temperature. A white solid precipitated from solution and was collected by frit filtration and washed with additional pentane. Yield: 4.8 g (90%).
Dimethylsilanediylbis! 1 -[2-isopropyl, 4-(2,3-dimethylphenyl)indene] }
Me2SiCl2 (1.2 g, 8.9 mmol) was dissolved in 80 mL of diethyl ether. While stirring, lithium! 1 -[2-isopropyl, 4-(2,3 -dimethy lpheny l)indenide]} (4.8 g,
18 mmol) was added as a dry powder and a few drops of THF were added to catalyze the reaction. The contents were allowed to stir overnight at room temperature. The solvent was removed in vacuo and the residue was taken up in pentane and filtered to remove LiCl salts. The pentane was removed in vacuo to yield a flaky white solid (5.2 g).
Dimethylsilanediylbis! 1 -[2-isopropyl, 4-(2,3-dimethylphenyl)indenyl]}zirconium dichloride
Dimethylsilanediylbis! l-[2-isopropyl,4-(2,3-dimethylphenyl)indene]} (5.2 g, 8.9 mmol) was dissolved in 60 mL of Et2O. While stirring, 7.2 mL of n-BuLi
(2.5M in hexane) was added and allowed to stir at room temperature for 2 hours. After this time, the solution was cooled to -35°C and ZrCl4 (2.1 g, 8.9 mmol) was added and allowed to stir at room temperature for 3 hours. The solvent was then removed in vacuo and the residue was taken up in a mixture of methylene chloride and pentane and filtered to remove LiCl salts. The filtrate was then concentrated and chilled to -35 °C to induce crystallization. 0.23 g (3.5%) of pure racemic compound was obtained.
Supported Metallocene Catalyst System 19
In a 100 mL round bottom flask dimethylsilanediylbis! 1- [2-isopropyl, 4- (2,3-dimethylphenyl)indenyl]}zirconium dichloride (0.066 g) was added to the above MAO-toluene solution (6.74 g, 7.2 mL) and stirred twenty minutes. The resultant mixture was filtered through a medium glass frit funnel and washed with toluene (14 mL). To the combined filtrates was added dehydrated silica (4.0 g, Davison 948 Regular, 600°C dehydration). This slurry was stirred for twenty minutes, then dried at 40 °C for two minutes under vacuum on a rotary evaporator until the liquid evaporated and then the solid was further dried a total of about two hours and twenty eight minutes. The supported catalyst was recovered as a red- purple, free flowing solid (5.81 g).
EXAMPLE 20 Supported Metallocene Catalyst System 20
In a 10-ml vial 2.71 g (0.535 mmol) of an 1 1.05 wt% solution of tris- (perfluorophenyl)borane in toluene was massed. 0.10 g (0.615 mmol) of N,N- dimethylaniline (Aldrich, 98+%) was added followed by 5.0 g of toluene. A pink solution resulted. This solution was pipetted into a 250 ml round bottom flask containing 5.0 g of silica (Grace Davison, calcined at 500°C with 3-wt% (NH4)2SiF ) and a magnetic stir bar. 10 g of toluene was used to rinse the vial, pipette, and the sides of the flask. The flask was heated to 50 °C in an oil bath.
The mixture was stirred for 38 minutes. 0.057 g (0.065 mmol) of dimethylsilanediylbis! 1 -[2-isopropyl,4-(2-biphenylyl)indenyl] } zirconium dimethyl was added to the flask as a solid to produce a brown slurry. Stirring was continued for 35 minutes at 50 °C. After this time, the stirring and heating were discontinued. The solvent was stripped in vacuo to give 5.25 g. Composition by mass balance: Zirconium: 0.012 mmol/g catalyst, Boron: 0.12 mmol/g catalyst.
EXAMPLE 21 Supported Metallocene Catalyst System 21 In a 100 mL round bottom flask dimethylsilanediyl{l-[2-isopropyl-4-(2- biphenylyl)indenyl]} zirconium dichloride (0.074 g) was added to the above MAO-toluene solution (6.74 g, 7.2 mL) and stirred twenty minutes. The resultant mixture was filtered through a medium glass frit funnel and washed with toluene (14 mL). To the combined filtrates was added dehydrated silica (4.0 g, Davison 948 Regular, 600°C dehydration). This slurry was stirred for twenty minutes, then dried at 40 °C for two minutes under vacuum on a rotary evaporator until the liquid evaporated and then the solid was further dried a total of about 2 hours and thirty one minutes. The supported catalyst was recovered as a light reddish purple, free flowing solid (5.28 g).
EXAMPLE 22
2-Isopropyl, 4-(2-biphenylyl)-indene
Magnesium (2.0 g, 83 mmol) and 2-bromobiphenyl (10 g, 43 mmol) were added together in 100 mL of diethyl ether and allowed to stir overnight at reflux to form a Grignard solution. 4-Chloro-2-isopropylindene (7.5 g, 434 mmol) and
NiCl2(PPh3)2 (1.5 g, 2.3 mmol) were dissolved in 150 mL of Et2O. The Grignard solution was added and the reaction was stirred overnight at reflux. After overnight stirring, the reaction was slowly quenched with H2O to neutralize unreacted Grignard. The solution was subsequently treated with 100 mL of 10% HCl(aq), and neutralized with saturated sodium bicarbonate aqueous solution. The organic layer was dried with magnesium sulfate and the solvent was removed by rotary evaporation. The remaining residue was loaded onto a silica gel column and eluted with hexane. Yield was 8.1 g (61%).
Lithium! 1 -[2-isopropyl, 4-(2-biphenylyl)indenide] }
2-Isopropyl, 4-(2-biphenylyl)-indene (4.0 g, 13 mmol) was dissolved in 100 mL of pentane. To this solution was added 5.2 mL of n-BuLi (2.5M in hexane) and the reaction was allowed to stir 4 hours at room temperature. A white solid precipitated from solution and was collected by frit filtration and washed with additional pentane. Yield: 2.7 g (67%).
Dimethylsilanediylbis { 1 - [2-isopropyl, 4-(2-biphenylyl)indene] }
Me SiCl2 (0.55 g, 4.3 mmol) was dissolved in 60 mL of diethyl ether. While stirring, lithium{ l -[2-isopropyl, 4-(2-biphenylyl)indenide] } (2.7 g, 8.6 mmol) was added as a dry powder and a few drops of THF were added to catalyze the reaction. The contents were allowed to stir overnight at room temperature. The solvent was removed in vacuo and the residue was taken up in pentane and filtered to remove LiCl salts. The pentane was removed in vacuo to yield a flaky white solid. Yield: 2.1 g (72%).
Dimethylsilanediylbis!! -[2-isopropyl, 4-(2biphenylyl)indenyl]} zirconium dichloride
Dimethylsilanediylbis! 1 -[2-isopropyl, 4-(2-biphenylyl)indene]} (2.1 g, 3.1 mmol) was dissolved in 60 mL of Et2O. While stirring, 2.5 mL of n-BuLi (2.5M in hexane) was added and allowed to stir at room temperature for 0.5 hours. After this time, the solution was cooled to -35°C and ZrCl4 (0.73 g, 3.1 mmol) was added and allowed to stir at room temperature for 3 hours. The solvent was then removed in vacuo and the residue was taken up in a mixture of methylene chloride and pentane and filtered to remove LiCl salts. The filtrate was then concentrated and chilled to -35 °C to induce crystallization. 0.29 g (11%) of pure racemic isomer was isolated.
Dimethylsilanediylbis!! -[2-isopropyl, 4-(2-biphenylyl)indenyl]} zirconium dimethyl
Dimethylsilanediylbis ! 1 - [2-isopropyl, 4-(2-biphenyly l)indenyl] } zirconium dichloride (0.4 g, 490 μmol) was dissolved in 50 mL of toluene. To this solution was added 1.8 mL of MeMgBr (3.0M in Et2O) and the reaction was stirred at 90°C for 5 hours. After this time, the reaction was cooled to room temperature and 10 mL each of SiCl and 1,4-dioxane was added. The solution was filtered through celite and the solvent was removed in vacuo. The resulting solids were washed with pentane. Yield: 0.18 g (44%).
Supported Metallocene Catalyst System 22 In a 100 mL round bottom flask dimethylsilanediylbis! 1 -[2-isopropyl, 4-
(2-biphenylyl)indenyl]} zirconium dimethyl (0.070 g) was added to the above MAO-toluene solution (6.74 g, 7.2 mL) and stirred twenty minutes. The resultant mixture was filtered through a medium glass frit funnel and washed with toluene (14 mL). To the combined filtrates was added dehydrated silica (4.0 g, Davison 948 Regular, 600°C dehydration). This slurry was stirred for twenty minutes, then dried at 40 °C for two minutes under vacuum on a rotary evaporator until the liquid evaporated and then the solid was further dried a total of about 2 hours and thirty four minutes. The supported catalyst was recovered as a light purple, free flowing solid (5.56 g).
POLYMERIZATIONS
Isotactic Polypropylene Homopolymer
The polymerization procedure for producing homopolymers with the above supported metallocene catalyst systems was as follows. In a clean, dry two liter autoclave which had been flushed with propylene vapor, TEAL (triethyl aluminum) scavenger (0.3 mL, 1.5M) was added. Hydrogen gas was added at this point. The reactor was closed and filled with 800 mL of liquid propylene. After heating the reactor to 70 °C , the catalyst was added by washing in with propylene
(200 mL). After the indicated time, typically one hour, the reactor was cooled, and the excess propylene vented. The polymer was removed and dried.
Isotactic Polypropylene Random Copolymer (RCP)
The polymerization procedure for producing ethylene random copolymers (RCP) with the above supported metallocene catalyst systems was as follows. In a clean, dry two liter autoclave which had been flushed with propylene vapor, TEAL scavenger (0.3 mL, 1.5M) was added. Hydrogen gas was added at this point, if used. The reactor was closed and filled with 800 mL of liquid propylene.
After heating the reactor to 60 °C , an overpressure of ethylene, as indicated by the "delta kPa", was slowly added while maintaining 60°C. The ethylene inlet was closed while the catalyst was added by washing in with propylene (200 mL). Immediately after addition the ethylene inlet was reopened and the desired overpressure of ethylene was maintained. After the indicated time, typically one hour, the reactor was cooled, and the excess propylene vented. The polymer was removed and dried. Impact Copolymers (ICP)
The polymerization procedure for producing ICP with the above supported metallocene catalyst systems was as follows. In a clean, dry two liter autoclave which had been flushed with propylene vapor, TEAL scavenger (0.3 mL, 1.5M) was added. Hydrogen gas was added at this point. The reactor was closed and filled with 800 mL liquid propylene. After heating the reactor to 70 °C, the catalyst was added by washing in with propylene (200 mL). After the indicated time, typically one hour, the reactor was vented to about 170 psig (1172 kPa) pressure and then an ethylene/propylene gas mixture was passed through the reactor at the rates indicated while maintaining 200 psig (1379 kPa). At the end of the gas phase stage, typically 90 to 150 minutes, the reactor was vented and cooled under N2. The granular ICP polymer was removed and dried.
POLYMER ANALYSIS
Results are shown in Tables 1 -22 (A and B) below. The numbering of the Tables corresponds to the numbering of the above Examples (Supported Metallocene Catalyst Systems). Molecular weight determinations were made by gel permeation chromatography (GPC) according to the following technique. Molecular weights and molecular weight distributions were measured using a Waters 150°C gel permeation chromatograph equipped with Shodex (Showa Denko) AT-80 M/S columns and a differential refractive index (DRI) detector operating at 145°C with 1,2,4-trichlorobenzene as the mobile phase at a 1.0 mL/min. flow rate. The sample injection volume was 300 microliters. The columns were calibrated using narrow polystyrene standards to generate a universal calibration curve. The polypropylene calibration curve was established using k = 8.33 X 10~5 and a = 0.800 as the Mark-Houwink coefficients. The numerical analyses were performed using Waters "Millennium" software.
DSC melting points were determined on commercial DSC instruments and were reported as the second melting point. The polymer sample was heated to 230.0°C for ten minutes and then cooled from 230°C to 50°C at 10°C/minute. The sample was held at 50°C for five minutes. The second melt was then recorded as the sample was heated from 50°C to 200°C at a rate of 10°C/minute. The peak temperature was recorded as the second melting point.
The results summarized in Table 21 C were obtained by following the procedures described in J.C. Randall, Polymer Sequence Determination: Carbon-
13 NMR Method, Academic Press New York 1978, supra.
ICP POLYMER EXTRACTION METHOD
The ICP polymer was dissolved in hot xylene and then allowed to cool overnight. After filtration the insolubles were dried. The xylene soluble portion was evaporated and the soluble material recovered. The IV (intrinsic viscosity) of the recovered soluble material was measured in decalin at 135°C by using known methods and instruments such as a Schott A VSPro Viscosity Automatic Sampler.
At very high ICP MFR this method can extract some low molecular weight isotactic PP and thus lower the observed IV.
ICP POLYMER FRACTIONATION METHOD
The ICP samples were sent to Polyhedron Laboratories, Inc. to be fractionated and analyzed by GPC. A general description of the procedure is found in J. C. Randall, J. Poly. Sci.: Part A Polymer Chemistry, Vol. 36, 1527- 1542 (1998), supra.
TABLE 1A
Dimethylsilanediylbis{l-[2-methyI, 4-phenylindenyl] Jzirconium dichloride
RUN # TEMP. C Caatt.. Y Yiieelldd E Effffiicciieennccyy C C22== H H22 T Tiimmee C? =/Ci
.mount (g) (Kg/g cat) (delta (mmole) split
(mg) kPa) (min.)
1 60 67 274.7 4.10 0 0 60 -
2 60 45 71.7 1.59 0 0 60 -
3 60 40 134.1 3.35 68.9 0 60 -
4 60 42 221.5 5.27 137.9 0 60 -
5 60 30 121.3 4.04 379.2 0 60 -
6 60 30 130.2 4.34 482.6 0 60 - t t
7 60 o
30 101.8 3.39 137.9 0 60 -
8 70 45 293.5 6.52 - 77.5 60 -
9 70 31 198.9 6.42 - 77.5 60 -
10 70 30 291.9 9.73 - 77.5 60/150 4.0/1.0
11 70 30 231.3 7.71 - 77.5 60/90 4.0/1.0
12 70 30 224.8 7.49 - 77.5 60/90 4.1/0.9
13 70 30 209.9 7.00 - 77.5 60/90 3.6/1.4
14 70 30 208.2 6.94 - 77.5 60/90 4.0/1.0
TABLE IB
Dimethylsilanediylbis{l-[2-methyl, 4-phenylindenyl] Jzirconium dichloride
RUN # Total Ethylene Ethylene in Total Final MFR Melting Point MW MWD IV of
(wt %) Rubber (wt%) Rubber (g/lO min.) (°C) (X 10"3) Copolymer (wt %) (dl/g)
1 0.16 149.2 600.0 2.00
2 - - - 0.54 148.2 664.9 1.92 -
3 0.67 - - 0.84 142.0 349.0 2.09 -
4 1.28 - - 2.57 138.4 280.0 1.95 -
5 3.77 - - 6.48 121.4 255.0 2.04 -
6 4.43 - - 5.95 116.0 301.0 2.30 -
7 1.44 - - 2.05 137.5 330.4 2.23 - )
■
8 - - - 99.6 150.3 120.6 3.01 -
9 - - - 58.95 150.9 135.7 3.15 -
10 13.23 49.20 26.89 178.5 151.2 81.2 3.37 0.7520
1 1 7.58 47.37 16.00 134.05 150.6 98.4 3.25 0.687
12 7.82 50.04 15.63 127.16 150.0 100.4 3.11 0.708
13 5.3 38.96 13.60 201.9 150.43 91.2 3.28 0.779
14 0.47 64.32 0.73 97.1 150.8 116.8 3.42 Not submitted
TABLE 2A
Dimethylsilanediylbis!!- [2-methyl, 4-(3-methylphenyl)indenyl]}zirconium dichloride
RUN # TEMP C Caatt.. Y Yiieelldd E Effffiicciieennccyy C C22== H H22 T Tiimmee Co=/Cτ.
Amount (g) (Kg/g cat) (delta (mmole) split
(mg) kPa) (min.)
15 60 45 106.7 2.37 0 0 60 -
16 60 46 232.5 5.05 68.9 0 60 -
17 60 45 285.1 6.34 137.9 0 60 -
18 60 21 132.0 6.29 241.3 0 60 -
19 70 20 220.1 11.01 - 77.5 60/90 4.0/1.0
20 70 22 197.9 9.00 - 54.3 60/90 4.0/1.0 to to
21 70 46 242.0 5 5..2266 - 5 544..33 3 300 - to
22 70 21 146.5 6.98 - 54.3 60 -
23 70 20 145.3 7.27 - 108.5 60 -
24 70 20 117.4 5.87 . 77.5 60 .
25 70 20 158.9 7.95 108.5 60/90 4.0/1.0
TABLE 2B
Dimethylsilanediylbis{l-[2-methyl, 4-(3-methylphenyl)indenyl]}zirconium dichloride
RUN # Total Ethylene Ethylene in Total Final MFR Melting Point MW MWD IV of
(wt %) Rubber (wt%) rubber (g/lO min.) (°C) (X 10"3) Copolymer (wt %) (dl/g)
15 0.08 149.43 797.1 2.05
16 0.15 - - 0.87 144.10 425.0 1.82 -
17 1.1 - - 2.48 139.97 318.2 1.82 -
18 2.0 - - 4.50 134.17 280.6 1.93 -
19 7.431 50.60 14.69 15.68 151.1 195.7 3.37 0.684
20 9.699 49.32 19.67 6.27 150.7 302.9 3.82 0.772 to to
21 - - - 2.48 151.03 334.5 2.26 -
22 - - - 1.61 150.97 336.3 2.22 -
23 - - - 91.78 151.90 125.0 3.24 -
24 - - - 39.82 151.63 154.3 2.76 -
25 6.454 51.06 12.64 Not submitted 151.3 83.6 3.11 0.832
TABLE 3A
Dimethylsilanediylbis{l-[2-methyl, 4-(3,5-dimethylphenyl)indenyl]}zirconium dichloride
Figure imgf000226_0001
26 60 45 72.7 1.6 0 0 60 -
27 60 45 111.9 2.5 34.5 0 60 -
28 60 47 155.6 3.3 68.9 0 60 -
29 60 46 204.9 4.5 137.9 0 60 -
30 60 45 244.5 5.4 241.3 0 60 -
31 70 30 251.2 8.4 - 54.3 60/90 4.0/1.0 t t
32 70 30 236.8 7.9 - 54.3 60/90 3.6/1.4 4-.
33 70 32 259.5 8.7 - 54.3 60/90 4.2/0.8
34 70 33 249.4 7.6 - 54.3 60/90 4.4/0.6
35 70 33 186.8 5.7 . 54.3 60 -
TABLE 3B
Dimethylsilanediylbis{l-[2-methyl, 4-(3,5-dimethylphenyl)indenyl]}zirconium dichloride
RUN Total Ethylene Ethylene in Total Final MFR Melting Point MW MWD IV Of
# (wt %) Rubber (wt%) rubber (g/lO min.) (°C) (X 10"3) Copolymer (wt %) (dl/g)
26 0.0245 150.9 937.7 2.10
27 - - - 0.17 148.3 671.3 2.15 -
28 0.18 - - 0.59 145.03 463.6 2.01 -
29 1.1 - - 2.68 140.9 303.8 1.89 -
30 1.8 - - 3.98 135.43 255.7 1.74 -
31 8.1 1 49.7 16.3 4.54 152.57 281.1 3.51 0.866
32 5.34 40.32 13.2 6.25 151.97 284.5 3.57 0.861 to to
33 9.98 58.47 17.1 7.07 152.43 220.4 3.00 1.420
34 14.42 61.66 23.4 19.43 152.1 179.4 2.57 1.091
35 - - - 1.79 151.30 327.9 1.98 .
TABLE 4A
Dimethylsilanediylbis{l-[2-methyl, 4-(2-methylphenyl)indenyl]}zirconium dichloride
Figure imgf000228_0001
36 60 47 33.0 0.70 0 0 60 -
37 60 45 118.7 2.64 68.9 0 60 -
38 60 45 197.7 4.39 137.9 0 60 -
39 60 47 340.7 7.25 241.3 0 60 -
40 70 33 273.4 8.28 - 77.5 60/90 4.0/1.0
41 70 20 222.9 11.15 - 77.5 60/90 4.0/1.0 to t
42 70 22 228.0 10.36 - 77.5 60/90 4.1/0.9
43 70 20 222.3 11.12 - 77.5 60/90 3.6/1.4
44 70 20 175.4 8.77 - 54.3 60/90 4.0/1.0
45 70 20 161.0 8.05 - 54.3 60/90 4.1/0.9
46 70 20 174.0 8.70 - 54.3 60/90 3.6/1.4
47 70 21 189.6 9.03 - 54.3 60/120 4.0/1.0
48 70 20 132.1 6.61 - 54.3 60 -
49 70 20 159.1 7.96 - 77.5 60.0 -
TABLE 4B
Dimethylsilanediylbis{l-[2-methyl, 4-(2-methylphenyl)indenyl]}zirconium dichloride
RUN # Total Ethylene Ethylene in Total Final MFR Melting Point MW MWD IV of
(wt %) Rubber ( t%) rubber (g/lO min.) (°C) (X 10'3) Copolymer (wt %) (dl/g)
36 0.09 146.5 912.2 2.17
37 0.67 - - 0.52 136.63 499.0 2.33 -
38 1.24 - - 0.61 132.57 449.8 2.22 -
39 2.1 - - 0.69 126.77 499.8 2.01 -
40 - - - 111.98 144.63 115.1 2.41 -
41 6.951 48.87 14.22 140.01 145.7 99.7 2.59 1.429
42 7.88 52.43 15.03 133.9 145.37 100.9 2.74 1.287 to to
43 5.576 38.33 14.55 83.2 144.90 111.8 2.34 1.046
44 7.353 48.96 15.02 29.14 145.10 143.3 2.50 1.446
45 8.809 51.90 16.97 20.42 145.17 154.3 2.42 1.448
46 6.013 35.55 16.91 35.55 144.97 151.8 2.32 1.355
47 10.84 47.31 22.91 20.36 145.63 152.6 2.39 1.648
48 - - - 26.76 146.17 179.9 2.64 -
49 - - - 95.55 145.97 124.3 2.96 _
TABLE 5A
Dimethylsilanediylbis{l-[2-methyl, 4-(2-ethylphenyl)indenyl]}zirconium dichloride
Figure imgf000230_0001
60 48 19.5 0.41 0 0 60 -
60 46 28.2 0.61 34.5 0 60 -
60 45 36.0 0.80 68.9 0 60 -
60 45 44.9 1.00 137.9 0 60 -
60 45 69.6 1.55 241.3 0 60 -
70 152 256.1 1.68 - 54.3 35/90 4.0/1.0 I t
70 75 00
228.9 3.05 - 54.3 60 -
70 74 337.4 4.56 - 54.3 60/90 4.0/1.0
70 33 134.7 4.08 - 54.3 60/90 4.0/1.0
70 33 118.8 3.60 - 54.3 60/90 3.6/1.4
70 31 123.0 3.97 - 54.3 60/90 4.4/0.6
70 31 130.8 4.22 - 54.3 60/90 4.2/0.8
70 31 85.9 2.77 - 54.3 60 -
TABLE 5B
Dimethylsilanediylbis{l-[2-methyl, 4-(2-ethylphenyl)indenyl]}zirconium dichloride
RUN # Total Ethylene Ethylene in Total Final MFR Melting Point MW MWD IV of
(wt %) Rubber (wt%) rubber (g/10 min.) (°C) (X 10-3) Copolymer (wt %) (dl/g)
50 0.038 147.97 786.3 2.14
51 Trace - - 0.088 144.3 670.7 2.60 -
52 0.83 - - 0.092 139.63 635.7 2.58 -
53 1.7 - - 0.16 134.17 621.5 2.21 -
54 2.6 - - 0.2 127.5 642.0 2.06 - to to
55 - - - 15.17 147.1 232.3 2.56 -
56 - - - 15.72 147.10 214.4 2.42 -
57 12.68, 50.79, 24.97, 18.43 147.77 160.7 2.49 1.889 12.74 50.59 25.18
58 7.107 48.48 14.66 97.17 145.7 103.1 2.64 1.788
59 6.874 38.31 17.94 31.95 145.83 136.9 2.50 1.746
60 12.59 60.64 20.76 48.37 145.63 130.2 2.57 2.15
61 9.74 52.29 18.63 52.52 146.03 133.8 2.42 2.02
62 - - - 34.83 146.03 172.6 2.43 .
TABLE 6A
Dimethylsilanediylbis{l-[2-methyl, 4-(2-isopropylphenyl)indenyl]}zirconium dichloride
Figure imgf000232_0001
63 60 46 15.1 0.33 0 60 -
64 70 21 63.3 3.01 54.3 60 -
65 70 60 243.1 4.05 54.3 60/90 4.0/1.0
66 70 61 159.5 2.61 54.3 60 -
67 70 61 221.4 3.63 54.3 60/90 3.6/1.4
68 70 61 199.8 3.28 54.3 60/90 4.2/0.8 to o
TABLE 6B
Dimethylsilanediylbis{l-[2-methyl, 4-(2-isopropylphenyl)indenyl]}zirconium dichloride
RUN # Total Ethylene Ethylene in Total Final MFR Melting Point MW MWD IV of (wt %) Rubber (wt%) rubber (g/lO min.) (°C) (XI 0-3) Copolymer (wt %) (dl/g)
63 - - - 0.099 148.23 690.1 2.38 -
64 - - - 125.8 144.70 115.0 2.59 -
65 14.64 51.63 28.36 9.8 145.03 167.1 2.83 2.34
66 - - - 40.59 144.77 146.2 3.04 -
67 9.487 41.48 22.87 24.72 144.23 158.1 2.60 1.94 to
68 13.26 54.58 24.29 15.4 145.3 167.6 2.77 ω
2.46
TABLE 7A
Dimethylsilanediylbis{l-[2-methyl, 4-(2-biphenylyl)indenyl]}zirconium dichloride
Figure imgf000234_0001
69 60 48 102.9 2.14 0 60 -
70 70 23 290.6 12.63 54.3 60/90 4.0/1.0
71 70 20 216.4 10.82 54.3 60 -
72 70 20 271.1 13.56 54.3 60/120 4.0/1.0
73 70 20 141.5 7.08 54.3 60/90 4.2/0.8
74 70 21 260.4 12.4 54.3 60/90 3.6/1.4 t
75 70 20 231.2 11.56 54.3 60/90 4.2/0.8
TABLE 7B
Dimethylsilanediylbis{l-[2-methyl, 4-(2-biphenylyl)indenyl]}zirconium dichloride
RUN # Total Ethylene Ethylene in Total Final MFR Melting Point MW MWD IV of
(wt %) Rubber (wt%) rubber (g/lO min.) (°C) (XI 0-3) Copolymer (wt %) . (dl/g)
69 0.052 148.63 772.9 1.92
70 6.066 46.64 13.01 19.18 150.30 156.5 2.35 1.338
71 - - - 12.93 150.70, minor 194.7 2.00 - 136.9
72 7.476 45.74 16.34 14.69 149.83 167.4 2.13 1.30
73 6.001 53.32 11.25 62.35 149.9 126.9 1.95 1.06 t
74 4.605 35.36 13.02 13.98 151.7 186.8 2.46 1.06
75 7.778 53.54 14.53 13.05 150.77 166.0 2.23 1.36
TABLE 8A
Dimethylsilanediylbis{l-[2-methyl, 4-(4-biphenylyl)indenyl]}zirconium dichloride
Figure imgf000236_0001
76 60 48 69.6 1.45 0 60 -
77 70 22 110.2 5.01 54.3 60 -
78 70 21 120.9 5.76 54.3 60/90 4.0/1.0
79 70 20 131.7 6.07 54.3 60/120 4.0/1.0
80 70 20 121.3 6.07 54.3 60/90 4.2/0.8
81 70 23 135.0 5.87 54.3 60/90 3.6/1.4 to
TABLE 8B
Dimethylsilanediylbis{l-[2-methyl, 4-(4-biphenylyl)indenyl]}zirconium dichloride
RUN # Total Ethylene Ethylene in Total Final MFR Melting Point MW MWD IV Of
(wt %) Rubber (wt%) rubber (g/lO min.) (°C) (XI 0-3) Copolymer (wt %) (dl/g)
76 0.046 145.57 662.3 2.06
77 - - - 4.36 147.3 . 244.6 2.23 -
78 4.18 56.56 7.39 13.17 148.5 185.0 3.30 0.79
79 8.58 52.12 16.46 29.02 148.43 191.2 3.69 0.62
80 10.31 56.37 18.29 23.12 149.9 177.2 2.99 0.81
81 5.535 42.06 13.16 18.13 148.3 218.0 3.87 0.69 to
TABLE 9A
Dimethylsilanediylbis{l-[2-methyl, 4-(4-tert-butylphenyl)indenyl]}zirconium dichloride
RUN TEMP Cat. Yield Efficiency H2 Time
# (°C) Amount (g) (Kg/g cat) (mmole) split
(mg) (min.)
82 60 48 9.9 0.21 0 60 83 70 30 27.2 0.91 54.3 60
TABLE 9B to
Dimethylsilanediylbis{l-[2-methyI, 4-(4-tert-butylphenyl)indenyl]}zirconium dichloride
RUN Final MFR Melting Point MW MWD # (g/10 min.) (°C) (XIO-3)
82 0.0725 150.9 979.3 2.68
83 33.04 152.9 159.7 3.03
TABLE 10A
Dimethylsilanediylbis{l-[2-methyl, 4-(2,3-dimethylphenyl)indenyl]}zirconium dichloride
Figure imgf000239_0001
84 60 45 26.2 0.58 0 60
85 70 20 67.8 3.39 54.3 60/90 4.0/1.0
86 70 60 262.2 4.37 54.3 60/90 4.0/1.0
87 70 60 174.8 2.91 54.3 60
88 70 60 212.5 3.54 54.3 60/90 4.1/0.9
89 70 60 255.1 4.25 54.3 60/90 3.6/1.4 to
90 70 60 264.0 4.40 54.3 60/120 4.0/1.0
91 70 61 205.9 3.38 62.0 60/90 4.0/1.0
92 70 62 257.8 4.16 69.8 60/90 4.0/1.0
93 70 61 199.5 3.27 77.5 60/90 4.0/1.0
94 70 61 213.4 3.50 93 60/90 4.0/1.0
TABLE 10B
Dimethylsilanediylbis{l-[2-methyl, 4-(2,3-dimethylphenyl)indenyl]}zirconium dichloride
RUN # T Toottaall EEtthhyylleennee E Etthhyylleennee iinn T Toottaall F Fiinnaall MMFFRR M Meellttiinngg PPooiinntt M MWW MWD IV Of
(wt %) Rubber (wt%) rubber (g/lO min.) (°C) (X 10"3) Copolym (wt %) (dl/g)
84 - - - 0.023 149.3 963.8 2.32 -
85 9.417 46.86 20.10 28.72 148.37 139.0 3.39 1.92
86 14.21 50.48 28.15 2.31 149.63 253.4 2.58 2.21
87 - - - 5.02 150.37 264.0 2.69 - minor 137.46
88 14.65, 52.46, 27.93, 2.54 150.37 263.8 2.75 2.232 14.64 52.37 27.95 to oo
89 12.99, 38.1, 34.09, 4.56 151.17 218.0 2.72 2.487 13.1 37.65 34.79
90 22.8, 53.16, 42.89, 3.64 150.3 205.8 3.30 2.268 22.45 52.62 42.66
91 15.81 51.87 30.48 9.77 149.57 165.6 2.54 1.968
92 20.94 51.96 40.30 5.47 150.37 206.4 3.14 1.558
93 13.24 51.07 25.93 40.22 149.83 131.2 3.58 2.007
94 12.18 45.24 26.92 39.73 149.03 150.3 4.28 2.71 1
TABLE IIA
Dimethylsilanediylbis{l-[2-methyl, 4-(2,4-dimethylphenyl)indenyl]}zirconium dichloride
Figure imgf000241_0001
95 60 47 41.6 0.89 0 60 -
96 70 32 322.9 10.09 54.3 60/120 4.0/1.0
97 70 20 168.2 8.41 54.3 60/90 4.0/1.0
98 70 20 180.1 9.01 54.3 60/90 4.1/0.9
99 70 20 177.1 8.86 54.3 60/90 3.6/1.4
100 70 20 181.0 9.05 54.3 60/120 4.0/1.0 to
101 70 21 138.2 6.58 54.3 60 -
TABLE 11B
Dimethylsilanediylbis{l-[2-methyl, 4-(2,4-dimethylphenyl)indenyl]}zirconium dichloride
RUN # Total Ethylene Ethylene in Total Final MFR Melting Point MW MWD IV Of
(wt %) Rubber (wt%) rubber (g/lO min.) (°C) (X 10"3) Copolymer
(wt %) (dl/g)
95 0.073 145.63 954.8 2.28
96 16.62 52.43 31.70 9.53 144.23 166.3 3.81 1.582
97 8.092, 48.83, 16.57, 24.3 144.23 153.1 2.21 1.047 8.171 49.08 16.64
98 7.83 54.21 14.44 76.69 143.1 117.7 2.36 1.89
99 5.484 39.52 13.88 67.85 144.03 132.6 2.66 1.28
100 9.509 50.14 18.96 41.15 144.3 122.4 2.43 1.46 to ^
101 - - - 72.39 144.83 132.3 2.25 -
TABLE 12A
Dimethylsilanediylbis{l-[2-methyl, 4-(2,6-dimethylphenyl)indenyl]}zirconium dichloride
Figure imgf000243_0001
102 60 46 6.9 0.15 0 0 60 -
103 60 45 95.4 2.12 68.9 0 60 -
104 60 46 110.0 2.39 137.9 0 60 -
105 60 45 99.6 2.21 241.3 0 60 -
106 70 22 37.5 1.70 - 54.3 60 -
107 70 77 87.7 1.14 - 54.3 60 - to
108 70 75 128.5 1.71 - 54.3 60/60 4.0/1.0
109 70 150 190.0 1.27 - 46.5 60/60 4.0/1.0
110 70 150 174.4 1.16 - 38.8 60/60 4.0/1.0
111 70 150 153.6 1.02 - 31.0 60/60 4.0/1.0
112 70 151 136.1 . 23.3 60/60 4.0/1.0
TABLE 12B
Dimethylsilanediylbis{l-[2-methyl, 4-(2,6-dimethylphenyl)indenyl]}zirconium dichloride
RUN # Total Ethylene Ethylene in Total Final MFR Melting Point MW MWD IV Of
(wt %) Rubber (wt%) rubber (g/lO min.) (°C) (X 10"3) Copolymer (wt %) (dl/g)
102 Not det. 148.1 307.0 3.52
103 1.20 - - 76.15 137.7 123.0 2.34 -
104 2.10 - - 68.21 133.63 144.2 2.59 -
105 3.70 - - 66.58 128.43 139.2 2.38 -
106 - - - 344.51 148.63 121.1 3.30 -
107 - - - 140.44 147.9 120.6 3.53 - to
108 5.044 43.14 11.69 596.49 147.3 77.3 5.66 0.678 t
109 9.546 45.29 21.08 136.53 147.9 102.6 3.63 0.844
110 1 1.86 44.81 26.47 108.99 148.17 105.2 2.33 0.778
11 1 12.06 45.83 26.31 103.02 147.03 106.1 3.69 0.834
1 12 12.89 44.96 28.67 78.06 147.57 114.1 3.12 0.456
TABLE 13A
DimethylsiIanediylbis{l-[2-methyl, 4-(2,5-dimethylphenyl)indenyl]}zirconium dichloride
RUN # TEMP C Caatt Y Yiieelldd E Effffiicciieennccyy C C22== H H22 T Tiimmee C? =/C
Amount (g) (Kg/g cat) (delta (mmole) split
(mg) kPa) (min.)
113 60 47 53.2 1.13 0 0 60 -
114 60 49 95.0 1.94 34.5 0 60 -
115 60 47 110.0 2.34 68.9 0 60 -
116 60 46 139.3 3.03 137.9 0 60 -
117 60 47 184.6 3.93 241.3 0 60 -
1 18 70 22 96.6 4.39 - 54.3 60 - to
119 •fc.
70 30 159.6 5.32 - 54.3 60/90 4.0/1.0
120 70 30 164.1 5.47 - 54.3 60/120 4.0/1.0
121 70 30 129.2 4.31 - 54.3 60 -
122 70 30 169.6 5.65 - 54.3 60/90 3.6/1.4
TABLE 13B
Dimethylsilanediylbis{l-[2-methyl, 4-(2,5-dimethylphenyl)indenyl]}zirconium dichloride
RUN # Total Ethylene Ethylene in Total Final MFR Melting Point MW MWD IV Of
(wt %) Rubber ( t%) rubber (g/lO min.) (°C) (X 10"3) Copolymer (wt %) (dl/g)
113 0.0275 149.77 815.9 2.09
114 0.1 - - 0.225 147.23 574.2 2.31 -
115 0.32 - - 0.51 144.03 460.2 1.90 -
1 16 1.2 - - 1.22 139.70 346.0 1.99 -
117 2.0 - - 4.78 134.83 297.2 2.00 -
118 - - - 1.07 151.03 385.5 2.23 - t j .
119 6.99 51.82 13.49 6.98 151.9 248.0 3.50 0.895 ■i .
120 9.66 50.95 18.84 5.33 152.17 236.8 3.20 1.161
121 - - - 2.02 151.37 357.3 2.27 -
122 4.968 42.16 11.78 7.77 152.03 220.0 3.28 0.826
TABLE 14A
Dimethylsilanediylbis{l-[2-methyl, 4-(2,3,4-trimethylphenyl)indenyl]}zirconium dichloride
Figure imgf000247_0001
123 60 45 44.8 1.00 0 60 -
124 70 21 98.2 4.68 54.3 60 -
125 70 20 131.5 6.58 54.3 60/90 1.0/4.0
126 70 20 134.3 6.72 54.3 60/90 3.6/1.4
127 70 21 109.4 5.21 54.3 60/90 4.1/0.9
128 70 21 137.4 6.54 54.3 60/120 4.0/1.0 to
4-.
TABLE 14B
Dimethylsilanediylbis{l-[2-methyl, 4-(2,3,4-trimethylphenyl)indenyl]}zirconium dichloride
RUN # Total Ethylene Ethylene in Total Final MFR Melting Point MW MWD IV Of
(wt %) Rubber (wt%) rubber (g/lO min.) (°C) (X 10"3) Copolymer (wt %) (dl/g)
123 No flow 148.43 820.1 2.18
124 - - - 2.28 148.77 306.1 2.41 -
125 10.9 47.12 23.13 1.12 148.70 310.4 2.60 2.08
126 7.221 37.00 19.51 2.04 149.23 273.7 3.21 1.82
127 10.50 51.77 20.28 1.23 149.50 302.4 2.90 1.99
128 16.71 48.63 34.36 0.91 148.97 260.1 2.43 2.63 to .fc.
TABLE 15A
Dimethy lsilanediylbis{l-[2-methyl, 4-(2,4,5-trimethylphenyl)indenyl]}zirconium dichloride
Figure imgf000249_0001
129 60 47 45.6 0.97 0 0 60 -
130 60 45 106.0 2.36 68.9 0 60 -
131 60 46 134.8 2.93 137.9 0 60 -
132 60 45 266.6 5.92 241.3 0 60 -
133 60 45 62.5 1.39 34.5 0 60 -
134 70 30 195.1 6.50 - 54.3 60/90 4.0/1.0 to
135 70 30 194.0 6.47 - 54.3 60 - ^1
136 70 30 242.3 8.08 - 54.3 60/90 3.6/1.4
137 70 31 216.0 6.97 - 54.3 60/90 4.2/0.8
138 70 30 231.5 7.72 - 54.3 60/90 4.4/0.6
139 70 31 270.2 8.72 . 54.3 60/120 4.0/1.0
TABLE 15B
Dimethylsilanediylbis{l-[2-methyl, 4-(2,4,5-trimethylphenyl)indenyl]}zirconium dichloride
RUN # Total Ethylene Ethylene in Total Final MFR Melting Point MW MWD IV Of
(wt %) Rubber (wt%) rubber (g/lO min.) (°C) (X 10"3) Copolymer (wt %) (dl/g)
129 0.048 148.60 914.8 2.46
130 - - - 0.37 139.98 625.1 3.14 -
131 - - - 0.43 133.78 568.4 2.58 -
132 - - - 0.52 129.92 545.2 2.32 -
133 - - - 0.165 144.04 672.0 3.05 -
134 9.56 47.94 19.94 2.50 148.3 274.4 2.98 1.93 t j .
135 - - - 9.68 148.17 232.7 2.80 - oo
136 6.492 37.9 17.13 4.54 149.77 235.0 2.55 1.676
137 10.69 55.99 19.09 8.04 147.85 203.2 3.06 1.880
138 18.17 62.73 28.97 2.24 147.17 264.9 2.70 2.077
139 10.56 50.91 20.74 15.56 147.30 168.9 3.04 1.825
TABLE 16A
Dimethylsilanediylbis{l-[2-methyl, 4-(2,3,5,6-tetramethylphenyl)indenyl]}zirconium dichloride
Figure imgf000251_0001
140 60 46 7.2 0.16 0 0 60
141 60 45 82.6 1.84 34.5 0 60 -
142 60 45 166.5 3.70 68.9 0 60 -
143 60 45 185.6 4.12 137.9 0 60 -
144 60 45 257.3 5.72 241.3 0 60 -
145 70 31 97.2 3.14 - 54.3 60/90 4.0/1.0 to
146 70 151 333.5 2.21 - 54.3 60/79 4.0/1.0
147 70 76 184.4 2.43 - 54.3 60/90 4.0/1.0
148 70 75 123.1 1.64 - 23.3 60/90 4.0/1.0
149 70 152 240.7 1.58 - 23.3 60/60 4.0/1.0
150 70 152 164.2 1.08 - 23.3 60 -
151 70 77 176.6 2.29 - 54.3 60 -
152 70 150 200.2 1.33 - 15.5 60/90 4.0/1.0
153 70 152 202.6 1.33 - 7.8 60/90 4.0/1.0
TABLE 16B
Dimethylsilanediylbis{l-[2-methyl, 4-(2,3,5,6-tetramethylphenyl)indenyl]}zirconium dichloride
RUN # Total Ethylene Ethylene in Total Final MFR Melting Point MW MWD IV Of
(wt %) Rubber (wt%) rubber (g/lO min.) (°C) (X 10"3) Copolymer (wt %) (dl/g)
140 149.24 181.4 1.85
141 - - - 66.43 144.10 120.8 2.00 -
142 - - - 70.51 139.03 118.4 1.92 -
143 - - - 78.03 134.57 119.3 2.13 -
144 - - - 63.79 130.23 136.4 1.92 -
145 4.699 to
47.11 9.97 1612.72 150.03 (155.5 65.7 2.95 0.807 ©
146 8.684 44.91 19.34 248.26 150.23 102.1 2.70 0.836
147 6.34 45.05 14.07 343.29 149.1 67.6 1.36 0.892
148 12.96 42.65 30.39 81.54 149.03 107.0 2.46 0.996
149 12.44 45.84 27.14 124.68 149.1 93.9 2.63 0.875
150 - - - 100.79 151.03 108.1 1.96 -
151 - - - Too fast 149.63 59.6 2.41 -
152 19.18 45.6 42.06 90.68 148.63 106.1 2.96 0.973
153 20.76 44.63 46.52 95.07 148.9 114.4 3.04 0.891
TABLE 17A
Dimethylsilanediylbis{l-[2-isopropyl, 4-(3-biphenylyl)indenyl]}zirconium dichloride
Figure imgf000253_0001
154 60 302 16.0 0.05 0 0 60 -
155 70 61 81.8 1.34 46.5 60/120 4.0/1.0
156 70 60 74.7 1.25 46.5 60/120 4.4/0.6
157 70 60 62.0 1.03 46.5 60 -
158 70 62 48.0 0.77 31.0 60 -
159 70 60 22.0 0.37 15.5 60 .
TABLE 17B
Dimethylsi lanediylbis{l-[2-isopropyl, 4-(3-biphenylyl)indenyl]}zirconium dichloride
RUN # Total Ethylene Ethylene in Total Final MFR Melting Point MW MWD IV Of
(wt %) Rubber (wt%) rubber (g/ 10 min.) (°C) (X 10'3) Copolymer (wt %) (dl/g)
154 15.26 150.37 227.8 2.04
155 5.011 41.67 12.03 118.14 151.97 134.6 2.88 1.88
156 9.911 53.91 18.38 52.09 152.77 164.9 3.71 2.95
157 - - - 259.61 150.83 104.3 2.38 -
158 - - - 116.54 150.97 125.2 2.28 -
159 - - - 102.01 151.17 128.0 2.05 to to
TABLE 18A
DimethylsilanediyIbis{l-[2-isopropyl, 4-(2-methylphenyl)indenyl]}zirconium dichloride
Figure imgf000255_0001
160 60 46 2.7 0.06 0 0 60
161 60 300 56.3 0.19 0 0 60
162 70 61 158.2 2.59 46.5 60/120 4.0/1.0
163 70 60 139.9 2.33 46.5 60
164 70 61 168.9 2.77 46.5 60/120 4.4/0.6
165 70 60 42.3 0.70 0 15.5 60 to
166 70 61 94.7 1.55 0 31.0 60
167 70 300 159.8 0.53 0 7.8 60
168 70 300 51.4 0.17 0 7.8 21
169 70 300 276.2 0.92 7.8 64/180 4.0/1.0
TABLE 18B
Dimethylsilanediylbis{l-[2-isopropyl, 4-(2-methylphenyl)indenyl]}zirconium dichloride
RUN Total Ethylene Ethylene in Total Final MFR Melting Point MW MWD IV of
# (wt %) Rubber (wt%) rubber (g/lO min.) (°C) (X10"3) Copolymer (wt %) (dl/g)
160 - - - Not submitted 153.5 178.2 2.13
161 - - - 30.48 154.83 197.2 2.12
162 3.584 43.25 8.29 971.02 152.17 75.6 2.50 1.121
163 - - - 1013.8 152.1 70.9 2.27 (157.17 minor
164 4.62 57.52 8.03 954.7 151.57 69.2 2.39 2.083
165 - - - 142.5 152.91 120.1 2.38
166 - - - 420.7 152.1 91.7 2.19
167 - - - 129.85 153.23 127.3 3.62
168 - - - 268.69 152.97 108.1 4.41
169 15.07, 48.96, 30.8, 11.94 154.1 238.1 14.49 1.993 14.24 47.85 29.8
TABLE 19A
Dimethylsilanediylbis{l-[2-isopropyl, 4-(2,3-dimethylphenyl)indenyl]}zirconium dichloride
Figure imgf000257_0001
170 60 306 55.0 0.18 0 60 -
171 70 122 130.8 1.07 7.8 60 -
172 70 122 123.9 1.02 7.8 60/90 4.0/1.0
173 70 122 106.3 0.87 7.8 60/90 4.1/0.9
174 70 122 88.9 0.73 7.8 60/90 3.6/1.4
175 70 121 108.3 0.89 7.8 60/120 4.0/1.0 to
176 70 123 146.8 1.19 15.5 60/90 4.0/1.0
177 70 124 140.7 1.13 15.5 60/90 4.2/0.8
178 70 122 92.2 0.76 15.5 60 -
TABLE 19B
Dimethylsilanediylbis{l-[2-isopropyl, 4-(2,3-dimethylphenyl)indenyl]}zirconium dichloride
RUN # Total Ethylene Ethylene in Total Final MFR Melting Point MW MWD IV Of
(wt %) Rubber (wt%) rubber (g/lO min.) (°C) (X 10'3) Copolymer (wt %) (dl/g)
170 16.93 153.1 190.3 2.09
171 - - - 70.15 151.63 157.1 2.78 -
172 10.54 44.28 23.80 10.07 153.03 215.0 3.21 2.18
173 16.1 1 47.0 34.28 2.21 152.5 262.2 3.52 2.68
174 8.036 31.63 25.41 19.22 151.7 191.5 2.83 2.35
175 18.04 44.83 40.24 1.56 152.23 261.1 3.96 1.62 to
176 7.447 43.78 17.01 32.4 151.77 170.8 2.94 1.73
177 14.43 49.56 29.12 7.46 152.3 213.5 3.53 1.99
178 - - - 110.54 151.3 119.2 2.43 .
TABLE 20A
Dimethylsilanediylbis{l-[2-isopropyl, 4-(2-biphenylyl)indenyl]}zirconium dimethyl/NCA
Figure imgf000259_0001
179 60 45 <0.5 <0.01 0 0 60
180 60 303 <0.5 <0.01 0 0 60
181 70 60 84.2 1.4 0 46.5 60
182 70 121 147.6 1.22 0 46.5 60
183 70 120 192.3 1.60 - 46.5 60/120 4.0/1.0
184 70 122 32.8 0.27 0 15.5 60 t
185 70 120 195.6 1.63 - 46.5 60/120 4.4/0.6 IΛ -J
186 70 123 198.8 1.62 0 46.5 60
187 70 121 42.0 0.35 0 23.3 60
TABLE 20B
Dimethylsilanediylbis{l-[2-isopropyl, 4-(2-biphenylyl)indenyl]}zirconium dimethyl/NCA
RUN # Total Ethylene Ethylene in Total Final MFR Melting Point MW MWD IV Of (wt %) Rubber (wt%) rubber (g/10 min.) (°C) (X 10"3) Copolymer (wt %) (dl/g)
179 180 181 390.37 158.38 88.1 2.17 182 228.3 . 158.3 101.0 2.19 183 4.283 37.52 11.42 165.76 157.77 103.7 2.51 1.54 184 99.02 158.57 132.0 2.07 185 4.304 55.95 7.69 148.85 157.7, minor 107.7 2.42 1.98 t
OO 160.4
186 511.88 156.84, minor 77.4 2.23 161.44
187 126.76 158.03 132.1 2.40
TABLE 21 A
Dimethylsilanediylbis{l-[2-isopropyl, 4-(2-biphenylyl)indenyI]}zirconium dichloride/MAO
Figure imgf000261_0001
188 60 45 5.6 0.12 0 0 60
189 60 300 83.7 0.28 0 0 60
190 70 60 188.0 3.13 - 46.5 60/120 4.0/1.0
191 70 61 201.6 3.30 - 46.5 60
192 70 60 234.8 3.91 - 46.5 60/120 4.4/0.6
193 70 60 66.9 1.12 - 15.5 60 to
194 70 61 107.5 1.76 - 31.0 60
195 70 301 125.8 0.42 - 7.8 25
196 70 63 150.8 2.39 - 46.5 60
197 70 150 222.9 1.49 - 31.0 60
198 70 150 233.0 1.55 . 31.0 60
TABLE 2 IB
Dimethylsilanediylbis{l-[2-isopropyl, 4-(2-biphenylyl)indenyl]}zirconium dichloride/MAO
RUN # Total Ethylene Ethylene in Total Final MFR Melting Point MW MWD IV of (wt %) Rubber (wt%) rubber (g/lO min.) (°C) (XI 0"3) Copolymer (wt %) (dl/g)
188 - 158.10 266.9 2.21 189 2.56 158.90 285.1 2.19 190 3.588 40.79 8.80 02.36 157.77 132.3 3.26 1.86 191 74.31 157.10 129.1 2.53 192 5.476 55.13 9.93 82.31 157.57 142.6 3.15 2.46 to
ON 193 11.04 157.90 211.8 2.55 O 194 24.95 156.70 169.1 2.41 195 39.42 157.57 168.4 2.12 196 58.6 156.04, minor 114.3 2.43 160.7
197 33.95 156.85, minor 149.7 2.30 160.14
198 35.57 157.25 150.7 2.30
TABLE 21C
Dimethylsilanediylbis{l-[2-isopropyl, 4-(2-biphenylyl)indenyl]}zirconium dichloride/MAO
RUN # Meso Run Diad Stereo 2,1 -Misinsertions 1,3-Misinsertions Xylene Xylene Length (%) Misinsertions /l 0000 Monomer /10000 Monomer Solubles Insolubles
(Monomer / 10000 Monomer Units Units (wt %) (wt %) Units) Units
191 245 99.6 23.9 0 16.7 0.53 99.64 t 197 278 99.6 20.0 0 15.9 0.87 99.09
TABLE 22A
Dimethylsilanediylbis{l-[2-isopropyl, 4-(2-biphenylyl)indenyl]}zirconium dimethyl/MAO
Figure imgf000264_0001
199 70 61 168.4 2.76 0 46.5 60
200 70 101 180.2 1.78 0 31.0 60 -
201 70 101 186.1 1.84 - 31.0 60 -
202 70 62 141.3 2.28 - 31.0 60/120 4.4/0.6
203 70 60 138.5 2.31 . 31.0 60/120 4.4/0.6 t to
TABLE 22B
Dimethylsilanediylbis{l-[2-isopropyl, 4-(2-biphenylyl)indenyI]}zirconium dimethyl/MAO
RUN # Total Ethylene Ethylene in Total Final MFR Melting Point MW MWD IV Of
(wt %) Rubber (wt%) rubber (g/lO min.) (°C) (X 10-3) Copolymer (wt %) (dl/g)
199 - - - 143.13 156.04, minor 175.9 21.02 - 160.17
200 - - - 38.98 160.37 149.9 2.22 -
201 - - - 26.82 155.71 153.4 2.31 -
202 5.817 55.61 10.46 26.41 157.77 172.5 3.29 3.14
203 5.549 56.39 9.84 44.55 157.77 165.6 2.99 2.85 t
The metallocenes in the above Examples and Tables are represented by formula (I) as follows:
M = zirconium,
R1 , R2= CI (methyl in Examples 20 and 22), R4, R5, R6, R7 = H
R , 113J = Me2Si
Figure imgf000266_0001
Me = Methyl; Et = Ethyl; iso-Pr = Isopropyl; tert-Bu = tert. Butyl; Ph = Phenyl

Claims

WHAT IS CLAIMED IS:
-i 1 9
1. A bridged bis(2-R -4-phenyl-indenyl)R R metallocene wherein:
1 ") the phenyl rings are substituted at the 2' positions (R ) by radicals which may be identical or different halogen atoms, Cι-Cι0 alkyl groups, C6-C] aryl groups, C2- Cio alkenyl groups, C7-C40 arylalkyl groups, C -C 0 alkylaryl groups, C8-C40 arylalkenyl groups, and -NR'2, -SR', -OR', -SiR'3, -OSiR'3 and -PR2 radicals; the radicals R3 are selected from hydrogen, halogen, Ci-Cio alkyl groups, C6-Cι4 aryl groups, C2-Cι0 alkenyl groups, C -C40 arylalkyl groups, C -C40 alkylaryl groups, C8-C40 arylalkenyl groups, and -NR'2, -SR', -OR', -SiR'3, -OSiR'3 and -PR'2 radicals wherein each R' is independently selected from halogen, Ci-Cio alkyl groups and C6-Cι4 aryl groups; provided that if R1 and R2 both are halogen and R13 is dimethylsilanediyl, then R3 is different from methyl and ethyl.
A compound of claim 1 represented by the formula:
Figure imgf000267_0001
wherein:
M1 is selected from titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten;
R1 and R2 are selected from hydrogen, halogen, hydroxy, Ci-Cio alkyl groups, Cp Cio alkoxy groups, C6-Cι4 aryl groups, C6-Cι4 aryloxy groups, C -Cι0 alkenyl groups, C7-C40 arylalkyl groups, C -C40 alkylaryl groups and C -C40 arylalkenyl
1 ? groups; or R and R are joined together to form a C4-C 0 alkanediyl group or a conjugated C4-C40 diene ligand which is coordinated to M1 in a metallacyclopentene fashion; or R and R represent a conjugated diene, optionally substituted with one or more groups independently selected from hydrocarbyl, trihydrocarbylsilyl and trihydrocarbylsilylhydrocarbyl groups, said diene having a total of up to 40 atoms not counting hydrogen and forming a π complex with M ; R is selected from hydrogen, halogen, Cι-Cι0 alkyl groups, C -Cι4 aryl groups, C2-Cιo alkenyl groups, C -C40 arylalkyl groups, C -C40 alkylaryl groups, C8-C 0 arylalkenyl groups, and -NR'2, -SR', -OR', -SiR'3, -OSiR'3 and -PR'2 radicals wherein each R' is independently selected from halogen, Cι-Cι0 alkyl groups and
1 9 1 ^
C6-Cι4 aryl groups; provided that if R and R both are halogen and R is dimethylsilanediyl, R is different from methyl and ethyl; R4, R5, R6 and R7 are each independently selected from hydrogen, halogen, Cι-C]0 alkyl groups, C6-Cι aryl groups, C2-Cι0 alkenyl groups, C7-C40 arylalkyl groups, C -C40 alkylaryl groups, C8-C40 arylalkenyl groups, and -NR'2, -SR', -OR', -SiR'3, -OSiR'3 and -PR'2 radicals wherein each R' is independently selected from halogen, Ci-Cio alkyl groups and C6-Cι4 aryl groups; or two or more adjacent radicals R , R and R together with the atoms connecting them may form one or more rings;
R8, R9, R10 and R1 1 are each independently as defined for R4, R5, R6 and R7, provided that two or more adjacent radicals R8, R9, R10 and R1 1 together with the atoms connecting them may form one or more rings ; R12 is selected from halogen, Ci-Cio alkyl groups, C6-Cι4 aryl groups, C2-Cι0 alkenyl groups, C -C 0 arylalkyl groups, C7-C40 alkylaryl groups, C8-C40 arylalkenyl groups, and -NR'2, -SR', -OR', -SiR3, -OSiR* 3 and -PR'2 radicals wherein each R' is independently selected from halogen, CI-CJO alkyl groups and C6-Cι aryl groups;
R13 is selected from
Figure imgf000269_0001
I I
I I -M3- M3- M3- -O-M3-O-
Figure imgf000269_0002
Figure imgf000269_0003
I I I I I I
-M3- C - -O-M3- - C — C - C —
R I15 RI16 R I15 R I15 RI15 RI15
-B(R14)-, -A1(R14)-, -Ge-, -Sn-, -O-, -S-, -SO-, -SO2-, -N(R14)-, -CO-, -P(R14)-
-P(O)(R «1'4x , 16
Figure imgf000269_0004
-B[N(SiR ,1'4*τR>1153rR>10s).2]-; wherein:
R14, R15 and R16 are each independently selected from hydrogen, halogen, Cι-C20 alkyl groups, C-C0 aryl groups, C!-C20 alkoxy groups, C-C20 alkenyl groups,
C-C40 arylalkyl groups, C8-C40 arylalkenyl groups and C7-C40 alkylaryl groups, or
R14 and R15, together with the atom(s) connecting them, form a ring; and
M is selected from carbon, silicon, germanium and tin; or
R is represented by the formula
Figure imgf000269_0005
wherein: R17, R18, R19, R20, R21, R22, R23 and R24 are each independently selected from hydrogen, halogen, hydroxy, Ci-Cio alkyl groups, Ci-Cio alkoxy groups, C6-Cι4 aryl groups, C6-Cι4 aryloxy groups, C2-C]0 alkenyl groups, C7-C 0 arylalkyl groups, C -C40 alkylaryl groups and C8-C 0 arylalkenyl groups; or two or more adjacent radicals R17, R18, R19, R20, R21, R22, R23 and R24, including R20 and R21, together with the atoms connecting them, form one or more rings; and M2 represents one or more carbon atoms, or a silicon, germanium or tin atom.
3. The compound of claim 2, wherein M1 is selected from titanium, zirconium and hafnium.
4. The compound of claim 1 or 2, wherein R and R are selected from chlorine, Cι-C6 alkyl groups, C6-Cι0 aryl groups, C -Cι2 arylalkyl groups and C7- C]2 alkylaryl groups.
1
5. The compound of claim 1 or 2, wherein R and R are methyl groups.
6. The compound of claim 4, wherein R is selected from C3-C6 alkyl groups and phenyl.
7. The compound of claim 4, wherein R3 is selected from branched C3-C4 alkyl groups.
8. The compound of claim 1 or 2, wherein R3 is an isopropyl group.
The compound of claims 2 to 8 , wherein R is hydrogen.
10. The compound of claim 3, wherein M is selected from carbon and silicon, and R14, R15 and R16 are independently selected from Cι-C4 alkyl groups and C6- Cio aryl groups.
11. The compound of claim 3, wherein R13 is represented by the formula
Figure imgf000271_0001
wherein:
R17, R18, R19, R20, R21, R22, R23 and R24 each are hydrogen; and
M2 represents a silicon atom.
1
12. The compound of any of claims 1 to 11 wherein R is selected from Cι-C6 alkyl groups and C6-Cιo aryl groups.
13. The compound of any of claims 1 to 12, wherein R12 is phenyl.
14. The compound of any of claims 2 to 13, wherein at least one of R and R is hydrogen.
15. The compound of any of claims 2 to 11, wherein R12 is CpC2 alkyl and R11 is different from hydrogen.
ά R
16. The compound of any of claims 2 to 15, wherein each of R and R is hydrogen.
17. The compound of claim 2, wherein R1 and R2 are selected from chlorine, methyl, neopentyl and benzyl, R3 is selected from C3-C4 alkyl groups, each of R4 and R8 is hydrogen, and R12 is selected from Cι-C alkyl groups and C6-Cιo aryl groups.
18. The compound of any of claims 2 to 17, wherein R is selected from branched C3-C alkyl groups and R12 is selected from C6-Cιo aryl groups.
19. The compound of any of claims 2 to 17, wherein R is selected from isopropyl, isobutyl, sec-butyl, tert-butyl and phenyl groups, and R12 is selected from n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, phenyl, tolyl, benzyl and naphthyl groups.
20. The compound of claim 2, wherein M1 is selected from zirconium and hafnium; R1 and R2 are selected from chlorine, Cι-C3 alkyl groups and C -Cι0 aryl groups; R3 is selected from C -C6 alkyl groups and C6-Cιo aryl groups; R4 and R8 are hydrogen; R5, R6, R7, R9, R10 and R11 are each independently selected from hydrogen and Cι-C alkyl groups; R is selected from C3-C alkyl groups and C6- Cio aryl groups; and R13 is selected from di(C,-C4alkyl)silanediyl, diphenylsilanediyl, (Cι-C4 alkyl)phenylsilanediyl, diphenylmethanediyl and C2-C alkanediyl and alkenediyl radicals and groups of the formula
Figure imgf000272_0001
wherein:
R17, R18, R19, R20, R21, R22, R23 and R24 are each independently selected from hydrogen, halogen and Cι-C3 alkyl groups; and
M2 represents a carbon or silicon atom. 1 "
21. The compound of claim 20, wherein R is selected from di(Cι-C4 alkyl)silanediyl, diphenylsilanediyl, (Cι-C alkyl)phenylsilanediyl, C -C4 alkanediyl and alkenediyl, di(Cι-C alkyl)amidoborane and bis[tri(C)-C4 alkyl)lsilyl]amidoborane radicals.
22. A compound represented by the formula:
Figure imgf000273_0001
wherein:
M1 is selected from titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten;
1 9
R and R are selected from hydrogen, halogen, hydroxy, Cι-Cι0 alkyl groups, Ci- Cio alkoxy groups, C6-Cι aryl groups, C6-Cι4 aryloxy groups, C2-C10 alkenyl groups, C -C40 arylalkyl groups, C7-C40 alkylaryl groups and C7-C40 arylalkenyl groups; or R1 and R2 are joined together to form an alkanediyl group or a conjugated C -C40 diene ligand which is coordinated to M1 in a metallacyclopentene fashion; or R1 and R2 represent a conjugated diene, optionally substituted with one or more groups independently selected from hydrocarbyl, trihydrocarbylsilyl and trihydrocarbylsilylhydrocarbyl groups, said diene having a total of up to 40 atoms not counting hydrogen and forming a π complex with M1;
R3 is selected from hydrogen, halogen, Cι-C10 alkyl groups, C -C] aryl groups, C2-Cιo alkenyl groups, C7-C40 arylalkyl groups, C7-C40 alkylaryl groups, C8-C40 arylalkenyl groups, and -NR'2, -SR', -OR', -SiR'3, -OSiR'3 and -PR'2 radicals wherein each R' is independently selected from halogen, Ci-Cio alkyl groups and C -Cι4 aryl groups;
R4, R5, R6 and R7 are each independently selected from hydrogen, halogen, Ci-Cio alkyl groups, C6-Cι4 aryl groups, C2-Cι0 alkenyl groups, C7-C40 arylalkyl groups, C7-C 0 alkylaryl groups, C8-C40 arylalkenyl groups, and -NR'2, -SR', -OR', -SiR'3, - OSiR'3 and -PR'2 radicals wherein each R' is independently selected from halogen, Ci-Ci0 alkyl groups and C6-Cι4 aryl groups; or two or more adjacent radicals R5,
R and R together with the atoms connecting them may form one or more rings; R8, R9, R10 and R1 1 are each independently as defined for R4, R5, R6 and R7, provided that two or more adjacent radicals R8, R9, R10 and R11 together with the atoms connecting them may form one or more rings;
1 R is selected from halogen, Cι-Cι0 alkyl groups, C6-Cι4 aryl groups, C2-Cι0 alkenyl groups, C7-C40 arylalkyl groups, C7-C40 alkylaryl groups, C8-C40 arylalkenyl groups, and -NR'2, -SR', -OR', -SiR'3, -OSiR'3 and -PR'2 radicals wherein each R' is independently selected from halogen, C1-C10 alkyl groups and C6-Cι4 aryl groups;
11 R is selected from groups of the formula
Figure imgf000275_0001
wherein:
R17, R18, R19, R20, R21, R22, R23 and R24 are each independently selected from hydrogen, halogen, hydroxy, Ci-Cio alkyl groups, Ci-Cio alkoxy groups, C -Cι4 aryl groups, C6-Cι4 aryloxy groups, C2-C10 alkenyl groups, C7-C40 arylalkyl groups, C7-C4o alkylaryl groups and C8-C40 arylalkenyl groups; or two or more adjacent radicals R17, R18, R19, R20, R21, R22, R23 and R24, including R20 and R21, together with the atoms connecting them, form one or more rings; and M represents a carbon, silicon or germanium atom.
23. The compound of claim 22, wherein R is selected from C3-C6 alkyl groups and phenyl.
24. The compound of claim 23, wherein R3 is an isopropyl group.
I 9
25. The compound of claim 22 or 23, wherein R is selected from Cι-C alkyl groups and C -Cι0 aryl groups.
26. The compound of any of claims 22 to 26, wherein R 12 i •s phenyl
27. The compound of claim 28, wherein each of R and R is hydrogen.
28. A catalyst composition comprising the product of a compound of claims 1 2 or 22 and a cocatalyst.
29. The catalyst composition of claim 28, which further comprises a support material.
30. The catalyst composition of claim 28, wherein the support material is selected from silica, alumina, silica-alumina, magnesium chloride and mixtures thereof.
31. A polymerization process comprising contacting, under polymerization conditions, one or more ethylenically unsaturated monomers and a catalyst composition, said catalyst composition comprising the product of a compound represented by formula (I) and a cocatalyst:
Figure imgf000276_0001
wherein:
M1 is selected from titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten; R1 and R2 are selected from hydrogen, halogen, hydroxy, Ci- o alkyl groups, d- Cio alkoxy groups, C6-Cι4 aryl groups, C6-Cj aryloxy groups, C2-C10 alkenyl groups, C7-C4o arylalkyl groups, C -C40 alkylaryl groups and C -C 0 arylalkenyl groups; or R1 and R2 are joined together to form a C4-C40 alkanediyl group or a conjugated C4-C40 diene ligand which is coordinated to M1 in a metallacyclopentene fashion; or R1 and R2 represent a conjugated diene, optionally substituted with one or more groups independently selected from hydrocarbyl, trihydrocarbylsilyl and trihydrocarbylsilylhydrocarbyl groups, said diene having a total of up to 40 atoms not counting hydrogen and forming a π complex with M l ;
R3 is selected from hydrogen, halogen, C1-C10 alkyl groups, C -C1 aryl groups, C2-C10 alkenyl groups, C7-C40 arylalkyl groups, C7-C40 alkylaryl groups, C8-C40 arylalkenyl groups, and -NR'2, -SR', -OR', -SiR'3, -OSiR'3 and -PR'2 radicals wherein each R' is independently selected from halogen, C1-C10 alkyl groups and
1 1 ^ C6-Cι4 aryl groups; provided that if R and R both are halogen and R is dimethylsilanediyl, R3 is different from methyl and ethyl;
R4, R5, R and R7 are each independently selected from hydrogen, halogen, C1-C10 alkyl groups, C6-Cι aryl groups, C2-C10 alkenyl groups, C7-C40 arylalkyl groups, C7-C40 alkylaryl groups, C8-C40 arylalkenyl groups, and -NR'2, -SR', -OR', -SiR'3, -OSiR'3 and -PR'2 radicals wherein each R' is independently selected from halogen, C1-C10 alkyl groups and C6-Cι aryl groups; or two or more adjacent radicals R5, R6 and R7 together with the atoms connecting them may form one or more rings; R8, R9, R10 and R11 are each independently as defined for R4, R5, R6 and R7, provided that two or more adjacent radicals R8, R9, R10 and R1 1 together with the atoms connecting them may form one or more rings ;
19
R is selected from halogen, C1-C10 alkyl groups, C6-C]4 aryl groups, C2-Cιo alkenyl groups, C7-C40 arylalkyl groups, C7-C40 alkylaryl groups, C8-C40 arylalkenyl groups, and -NR'2, -SR', -OR', -SiR'3, -OSiR*3 and -PR'2 radicals wherein each R' is independently selected from halogen, C1-C10 alkyl groups and
C6-C]4 aryl groups; R13 is selected from
Figure imgf000278_0001
I
-M3- -M3- M3- -O-M3-O-
Figure imgf000278_0002
Figure imgf000278_0003
I I I I I -M3- C - -O-M3- C - C - C -
Figure imgf000278_0004
-B(R14)-, -A1(R14)-, -Ge-, -Sn-, -O-, -S-, -SO-, -SO2-, -N(R14)-, -CO-, -P(R14)-
-P(O)(R14)-, -B(NR14R15)- and -B[N(SiR14R15R16)2]-; wherein:
R14, R15 and R16 are each independently selected from hydrogen, halogen, Cι-C20 alkyl groups, C6-C30 aryl groups, Cι-C20 alkoxy groups, C2-C 0 alkenyl groups,
C7-Q0 arylalkyl groups, C8-C 0 arylalkenyl groups and C7-C 0 alkylaryl groups, or
R14 and R15, together with the atom(s) connecting them, form a ring; and
M3 is selected from carbon, silicon, germanium and tin; or
R is represented by the formula
Figure imgf000278_0005
wherein:
R17, R18, R19, R20, R21, R22, R23 and R24 are each independently selected from hydrogen, halogen, hydroxy, C1-C10 alkyl groups, C1-C10 alkoxy groups, C6-Cι4 aryl groups, C6-Cι4 aryloxy groups, C2-Cι0 alkenyl groups, C7-C40 arylalkyl groups, C7- 0 alkylaryl groups and C8-C40 arylalkenyl groups; or two or more adjacent radicals R17, R18, R19, R20, R21, R22, R23 and R24, including R20 and R21, together with the atoms connecting them, form one or more rings; and M2 represents one or more carbon atoms, or a silicon, germanium or tin atom.
32. The process of claim 31, wherein R1 and R2 are selected from chlorine, C\- C6 alkyl groups, C6-Cι0 aryl groups, C7-Cι2 arylalkyl groups and C7-Q2 alkylaryl groups.
33. The process of claims 31 or 32, wherein R3 is selected from C3-C6 alkyl groups and phenyl.
34. The process of claims 31 or 32, wherein R3 is an isopropyl group.
I 9 35. The process of any of claims 31 to 34, wherein R is selected from Cι-C6 alkyl groups and C -Cι0 aryl groups.
19
36. The process of any of claims 31 to 34, wherein R is phenyl.
37. The process of claims 31 or 32, wherein R3 is selected from isopropyl, isobutyl, sec-butyl, tert-butyl and phenyl groups, and R12 is selected from n- propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, phenyl, tolyl, benzyl and naphthyl groups.
38. The process of any of claims 31 to 37, wherein the catalyst composition further comprises a support material.
39. The process of claim 38, wherein the catalyst composition further comprises an inorganic support material.
40. The process of any of claims 31 to 39, wherein said monoolefms comprise compounds of the formula RaCH=CHRb wherein Ra and Rb are each independently selected from hydrogen, alkyl and alkenyl radicals having 1 to 14 carbon atoms or, together with the carbon atoms to which they are connected, form a ring having 4 to 8 carbon atoms.
41. The process of claim any of claims 31 to 39, wherein said ethylenically unsaturated monomers consist essentially of ethylene and/or propylene.
42. The process of any of claims 31 to 41 , wherein said process is carried out at a temperature ranging from 30° C to 80° C.
1 9
43. The process of claim 31 , wherein R and R are selected from chlorine, Cj- C6 alkyl groups, C6-Cι0 aryl groups, C7- 2 arylalkyl groups and C7-Cι2 alkylaryl groups, R is selected from C3-C6 alkyl groups and phenyl, each of R and R is hydrogen, R12 is selected from n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, phenyl, tolyl, benzyl and naphthyl groups, the cocatalyst is selected from compounds comprising noncoordinating anions, alumoxanes and mixtures thereof, wherein the catalyst composition further comprises a support material selected from silica, alumina, silica-alumina, magnesium chloride and mixtures thereof, and wherein said one or more ethylenically unsaturated monomers comprise at least ethylene and propylene.
44. A polymerization process comprising contacting, under polymerization conditions, one or more ethylenically unsaturated monomers and a catalyst composition, said catalyst composition comprising the product of a compound represented by formula (I) and a cocatalyst:
Figure imgf000281_0001
wherein:
M1 is selected from titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten;
I 9
R and R are selected from hydrogen, halogen, hydroxy, Cι-Cι0 alkyl groups, Cp Cio alkoxy groups, C6-Cι aryl groups, C6-Cι aryloxy groups, C2-C10 alkenyl groups, C7- 0 arylalkyl groups, C7-C o alkylaryl groups and C7-Q0 arylalkenyl
1 9 groups; or R and R are joined together to form an alkanediyl group or a conjugated C4-C 0 diene ligand which is coordinated to M1 in a metallacyclopentene fashion; or R1 and R2 represent a conjugated diene, optionally substituted with one or more groups independently selected from hydrocarbyl, trihydrocarbylsilyl and trihydrocarbylsilylhydrocarbyl groups, said diene having a total of up to 40 atoms not counting hydrogen and forming a π complex with M1;
R3 is selected from hydrogen, halogen, C1-C10 alkyl groups, C6-Cι4 aryl groups, C2-Ci0 alkenyl groups, C7-C40 arylalkyl groups, C7-C40 alkylaryl groups, C8-C40 arylalkenyl groups, and -NR'2, -SR', -OR', -SiR'3, -OSiR'3 and -PR'2 radicals wherein each R' is independently selected from halogen, Cι-Cι0 alkyl groups and C6-C] aryl groups;
R4, R5, R6 and R7 are each independently selected from hydrogen, halogen, Cι-Cι0 alkyl groups, C6-Cι aryl groups, C2-Cι0 alkenyl groups, C7-C40 arylalkyl groups, C7-C 0 alkylaryl groups, C8-C40 arylalkenyl groups, and -NR'2, -SR', -OR, -SiR'3, - OSiR'3 and -PR'2 radicals wherein each R' is independently selected from halogen, C1-C10 alkyl groups and C6-Cι4 aryl groups; or two or more adjacent radicals R5, R6 and R7 together with the atoms connecting them may form one or more rings; R8, R9, R10 and R11 are each independently as defined for R4, R5, R6 and R7, provided that two or more adjacent radicals R8, R9, R10 and R11 together with the atoms connecting them may form one or more rings;
R12 is selected from halogen, Cι-Cι0 alkyl groups, C6-Cι4 aryl groups, C2-Cι0 alkenyl groups, C7-C40 arylalkyl groups, C7-C40 alkylaryl groups, C -C 0 arylalkenyl groups, and -NR'2, -SR', -OR', -SiR* 3, -OSiR'3 and -PR2 radicals wherein each R' is independently selected from halogen, C1-C10 alkyl groups and C -Cι4 aryl groups; R13 is selected from groups of the formula
Figure imgf000282_0001
wherein:
R17, R18, R19, R20, R21, R22, R23 and R24 are each independently selected from hydrogen, halogen, hydroxy, C1-C10 alkyl groups, Cι-Cι0 alkoxy groups, C6-Cι aryl groups, C6-C]4 aryloxy groups, C2-Q0 alkenyl groups, C7-C40 arylalkyl groups, C7-C40 alkylaryl groups and C8-C 0 arylalkenyl groups; or two or more adjacent radicals R17, R18, R19, R20, R21, R22, R23 and R24, including R20 and R21, together with the atoms connecting them, form one or more rings; and M represents a carbon, silicon or germanium atom.
45. A polymer composition comprising:
(a) propylene polymer comprising at least 99 % by weight of units derived from propylene and having a melting point of at least 155° C; and
(b) olefin copolymer comprising from 40 to 70 % by weight of units derived from propylene and having an intrinsic viscosity of at least 1.8; the composition made with a single catalyst composition.
46. The polymer composition of claim 45, wherein component (a) is selected from homopolypropylene and copolymers of propylene and at least one monoolefin selected from ethylene and oc-olefins having from 4 to 12 carbon atoms, said copolymers containing at least 99.5 % by weight of units derived from propylene.
47. The polymer composition of claims 45 or 46, wherein component (b) comprises from 30 to 60 % by weight of units derived from ethylene.
48. The polymer composition of claim 47, wherein components (a) and (b) together contain a total of 1.5 to 20 % by weight of units derived from ethylene.
49. The polymer composition of any of claims 45 to 48, wherein component (a) has a melting point of at least 156° C.
50. The polymer composition of any of claims 45 to 49, wherein component
(a) has a melting point of at least 157° C.
51. The polymer composition of any of claims 45 to 49, wherein component
(b) has an intrinsic viscosity of at least 2.0.
52. The polymer composition of any of claims 45 to 49, wherein component (b) has an intrinsic viscosity of at least 2.2.
53. The polymer composition of any of claims 45 to 52, wherein the composition has a Mw/Mn of not higher than 3.5.
54. The polymer composition of any of claims 45 to 52, wherein the composition has a Mw/Mn of not higher than 3.0.
55. The polymer composition of any of claims 45 to 54, wherein component (a) is selected from homopolypropylene and copolymers of propylene and at least one monoolefin selected from ethylene and α-olefins having from 4 to 12 carbon atoms, said copolymers containing at least 99.5 % by weight of units derived from propylene, component (b) comprises from 30 to 60 % by weight of units derived from ethylene, and components (a) and (b) together contain a total of 1.5 to 20 % by weight of units derived from ethylene, wherein component (a) has a melting point of at least 157° C and component (b) has an intrinsic viscosity of at least 2.0, and wherein the composition has a Mw/Mn of not higher than 3.5.
56. The polymer composition of any of claims 45 to 55, wherein the catalyst composition is supported.
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