MXPA00002638A - Bimetallic complexes and polymerization catalysts therefrom - Google Patents

Abstract

Group 3-6 or Lanthanide metal complexes possessing two metal centers, catalysts derived therefrom by combining the same with strong Lewis acids, Bronsted acid salts, salts containing a cationic oxidizing agent or subjected to bulk electrolysis in the presence of compatible, inert non-coordinating anions and the use of such catalysts for polymerizing olefins, diolefins and/or acetylenically unsaturated monomers are disclosed.

Description

BIMETALLIC COMPLEXES AND POLYMERIZATION CATALYSTS OF THEM BACKGROUND OF THE INVENTION This invention relates to certain lanthanide or group 3,4 metal complexes possessing two metal centers and with polymerization catalysts obtained therefrom. In one form this invention relates to such metal complexes per se. In another embodiment of the claimed invention, the complexes can be activated to form catalysts for the polymerization of olefins. Also included in the invention are processes for preparing such complexes and methods for using the catalysts in addition polymerizations. The transition metal complexes of group 4 bicyclopentadienyl in which the metal is in the formal oxidation state +4, +3 or +2, and the olefin polymerization catalysts formed therefrom by combination with an activating agent, for example, alumoxane or ammonium borate, are well known in the art. Thus, US Pat. No. 3,242,099 describes the formation of olefin polymerization catalysts by the combination of bicyclopentadienyl metal dihalides with alumoxane. U.S. Patent No. 5,198,401 discloses metal complexes from which transition of tetravalent bicyclopentadienyl group 4 and polymerization catalysts from olefin obtained by converting such complexes into cationic forms in combination with a non-coordinating anion. Particularly preferred catalysts are obtained by the combination of salt is ammonium borate with hafnium, zirconium and bicyclopentadienyl titanium complexes. Among the many suitable complexes disclosed are the bis (cyclopentadienyl) zirconium complexes containing a diene linkage bound to the transition metal through p-bonds wherein the transition metal is in its highest formal oxidation state. R. Mülhaupt, et al., J Organomet. Chem., 460, 191 (1993), reported on the use of certain binuclear zirconocene derivatives of dicyclopentadienyl-1,4-benzene as channeled once for the polymerization of propylene. Metal complexes of compressed geometry, including titanium complexes, and methods for their preparation are disclosed in the serial US patent application n. 545,403, filed July 3, 1990 (EP-A-416,815); US-A-5,064,802, US-A-5,374,696, US-A-5, 055,438, US-A-5, 057,475, US-A-5,096,867, and US-A-5,470,993. Metal complexes of the compressed geometry type containing two metal centers joined by a dianionic junction separated from and not connected to the linking groups in such complexes containing delocalized p-electrons, have been previously taught, but not exemplified, in USP 5,055,438. Finally, EP-A-739,897 discloses certain multi-center metal complexes, wherein each metal atom was bonded through a bridging group generically described as a p-ligand or other electron donor.

Compendium of the invention The present invention relates to bimetallic complexes corresponding to the formula: wherein: M and 'are independently a 3,4,5,6 group or lanthanide metals, L is a divalent group (or trivalent group if linked to Q) having up to 50 non-hydrogen atoms and containing a p-system aromatic through which the group is attached to M, said L also being attached to Z; L 'is a monovalent group or a divalent group (if it is attached to L "or Q), or a trivalent group (if it is attached to both L" and Q) having up to 50 non-hydrogen atoms and containing one system -p aromatic through which the group is linked to M '; L "is a monovalent or divalent group (if it is attached to L" or Q), or a trivalent group (if it is attached to both L "and Q) having up to 50 atoms that are not hydrogen and containing an aromatic p-system through which the group is bound to M ', or L "is a portion comprising boron or a member of group 14 of the Periodic Table of the Elements, and optionally also comprising nitrogen, phosphorus, sulfur or oxygen, said L" having up to 20 non-hydrogen atoms; Z is a portion comprising boron or a member of group 14 of the Periodic Table of the Elements, and optionally also comprising nitrogen, phosphorus, sulfur or oxygen, said Z having up to 20 non-hydrogen atoms; X and X 'independently in each occurrence are anionic linking groups having up to 40 atoms exclusive of the class of linkages containing an aromatic p-system through which group is attached to M or M', optionally two X groups or two groups X 'together form a C4-4o conjugated or non-conjugated diene optionally substituted with one or more hydrocarbyl, silyl, halocarbyl or halohydrocarbyl groups; X "independently in each occurrence is a neutral binding compound having up to 20 atoms, Q is a divalent anionic linking group attached at a terminal to both Z and L and attached at the remaining terminal to both L 'and L", said Q having up to 20 atoms that are not hydrogen; x and x 'are independently integers from 0 to 3, selected to provide load balance; Y X "is a number from 0 to 3. Furthermore, according to the present invention a composition of matter useful as an addition polymerization catalyst is provided comprising: 1) at least one bimetallic complex (I) as already disclosed , Y 2) one or more activating cocatalysts, the molar ratio of 1) to 2) being from 1: 10,000 to 100: 1 or the product of the reaction formed by converting 1) to an active catalyst by the use of an activating technique. Furthermore, according to the present invention there is provided a polymerization process of one or more polymerie addition monomers comprising contacting said monomer or a mixture of said monomers with a catalyst comprising the aforementioned composition of matter. Finally, the present invention also relates to new methods for preparing the complexes including the following schematic reaction: The invented catalyst compositions allow the preparation of polymer blends of a single monomer or of a mixture of monomers thereby directly forming a polymer mixture in the reactor. This result is accentuated when different metals, different valences of metals or different bonding groups are used at the two metal centers. Alternatively, the invention allows an increase in the incorporation of long chain crosslinking in a polymer formed from a single monomer, especially ethylene, or a monomer mixture, due to the selection of a metal center adapted to form oligometric products terminated by functionality. vinyl in combination with a second metal center adapted to form high molecular weight polymers and adapted for the incorporation of long chain α-olefins in a polymer.

Detailed description Any reference to the Periodic Table of the Elements herein shall refer to the Periodic Table of the Elements published and registered by CRC Press. Inc., 1989. Also any reference to a Group or Groups will be to the Group or Groups as reflected in the Periodic Table of the Elements using the IUPAC system to number groups. The preferred metal coordination complexes according to the present invention correspond to the following formulas: (X)? M wherein Z, M, M ', X, X', x and x 'are as previously defined; Z 'is the portion comprising Boron or a member of the Group 14 of the Periodic Table of the Elements, and optionally also comprising nitrogen, phosphorus, sulfur or oxygen, said Z 'having up to 20 non-hydrogen atoms; Cp and Cp 'are cyclic C5R'4 groups bonded to Z or Z' respectively u bound to M or M 'respectively by means of delocalized p-electrons, where R' independently of each occurrence is hydrogen, hydrocarbyl, silyl, halo, fluorocarbyl, hydrocarbyloxy, hydrobisybisiloxy, N, N-di- (hydrocarbylsilyl) amino, N-hydrocarbyl-N-silyloamino, N, N-di (hydrocarbyl) amino, hydrocarbylene amino, di (hydrocarbyl) phosphino, hydrocarbyl sulfide; or hydroxycarbyloxy-substituted hydrocarbyl, said R 'having up to 20 non-hydrogen atoms, and optionally, two such R' substituents can be linked thereby causing Cp and Cp 'to have a fused ring structure, more optionally, Cp or Cp 'each independently is a trivalent derivative of the already identified group C5R'4 which is also linked to Q and an R' in each of Cp or Cp 'is a covalent linkage to Q; Q is a cyclic or linear hydrocarbylene, or a silane group, or a nitrogen, oxygen or substituted halo derivative thereof, said Q having up to 20 non-hydrogen atoms. The most preferred metal coordination complexes according to the present invention correspond to the formula: R 'R' wherein: R 'in each occurrence is hydrogen, hydrocarbyl, silyl, germyl, halo, cyano, halohydrocarbyl, hydrocarbyloxy, hydrocarbyloxy, di (hydrocarbylsilyl) amino, hydrocarbylsilyloamino, di (hydrocarbyl) amino, hydrocarbylene amino, di (hydrocarbyl) phosphino, hydrocarbyl sulfide; or hydrocarbyloxy-substituted hydrocarbyl, said R 'having up to 20 non-hydrogen atoms and optionally two R' groups together form a divalent derivative thereof connected to adjacent positions of the cyclopentadienyl ring thereby forming a fused ring structure, or R 'in an occurrence by cyclopentadienyl system is a covalent bond with Q; Z and Z 'independent of each occurrence are -Z * Y-, where: Y 'is -O-, -S-, -NR "-, -PR" -, OR "-, or -NR" 2 (and with respect to -OR "and -NR" 2, a union is a dative union through the available electron pair), where R "is hydrogen, hydrocarbyl, silyl, or silylohydrocarbyl of up to 12 non-hydrogen atoms, or R" is a covalent bond to Q, and Z * is SiR * 2, CR * 2, SiR * 2 SiR * 2, CR * 2 CR * 2, CR * = CR *, CR * 2SiR * 2 or GeR * 2; wherein R * in each occurrence is independently hydrogen, hydrocarbyl, silyl, halogenated alkyl, or halogenated aryl, said R * having up to 12 non-hydrogen atoms. The most highly preferred metal coordination complexes are amidosilane- or amidoalkanediyl compounds-corresponding to the formula: R 'R' wherein: Q is a hydrocarbylene, linear or cyclic silane group, or a nitrogen or oxygen containing a derivative thereof, M 'is Ti, Zr, Hf, Se, yttrium, or La; R 'is as already defined, X and X' are C1-10 hydrocarbyl; and Y'Z * is -NR * - (ER '") m, where E is independent of each occurrence of silicon or carbon, R" is C1-10 hydrocarbyl or a covalent bond to Q; R "'is d-4 alkyl, and m is an integer from 1 to 10. Preferably, R' is independently at each occurrence hydrogen, hydrocarbyl, silyl, fluorophenyl, hydrocarbyloxy, N, N-di (hydrocarbyl) amino, hydrocarbyloamino, or hydrocarbyloxy-substituted hydrocarbyl, said R 'having up to 20 non-hydrogen atoms, or two adjacent R' groups are joined as part of a fused ring system. More preferably, R 'is hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, (including all isomers where appropriate), cyclopentyl, cyclohexyl, norbornyl, benzyl, phenyl, N, N-di (methyl) amino, pyrrylyl, pyrrolidinyl, or two R 'groups are attached, the whole group C5R'4 thereby forming an indenyl, tetrahydroindenyl, fluorenyl, tetrahydrofluoroenyl, indacenyl or octahydrofluoroenyl group, or a C ^ -β hydrocarbyl-substituted, N, N -di (methyl) amino-substituted, or substituted pyrrolyl derivative thereof. Example of groups X or X 'suitable for all The aforementioned structural descriptions of the invention include unique atomic groups including hydride or halide, as well as multi-atomic groups such as hydrocarbyl, hydrocarbyloxy, dihydrocarbylamido (including cyclic hydrocarbylene groups) and halo, amino or phosphino substituted derivatives thereof, said multi groups -atomics containing up to 20 atoms that are not hydrogen. Specific examples include chloride, methyl, benzyl, allyl, N, N-dimethylamido, pyrrolinated, pyrrolidinated, (N, N-dimethylamino) benzyl, phenyl, methoxide, ethoxide, isopropoxide and isobutoxide. More preferably X and X 'are chloride, methyl, N, N-dimethylamido, or benzyl. In embodiments where two X or where two X 'groups together form a diene group or substituted diene group, such a group can form a p-complex with M or M' or the diene can form an s-complex with M or M ' In such complexes M and M 'are preferably Group 4 metals, most preferably Ti. In such complexes in which the diene is associated with the metal as an s-complex, the metal is in the formal +4 oxidation state and the diene and the metal together form a metallocyclopentene. In such complexes in which the diene is associated with the metal as a p-complex, the metal is in the formal oxidation state + 2, and the diene normally assumes a s-trans configuration or a s-cis configuration in the which the lengths of union between the metal and the four carbon atoms of the conjugated diene are almost equal. The dienes of the complexes where the metal is located in a state of formal oxidation of +2 are coordinated through p-complexation through double bonds of dienes and not through a resonance form of metallocycle containing s-junctions. The nature of the binding is determined by an X-ray crystallography or by an NMR spectral characterization according to the techniques of Yasuda, et al. Oraanometallics, 1, 388 (1982), (Yasuda I); Yasuda et al. , Acc, Chem, Res., 18, 120 (1985), (Yasuda II); Er er, et al., Adv. Oraanomet Chem .: 24, 1 (1985) (Erker et al. (I)); and US-A-5, 198,401. By the term "p-complex" we mean that both the donation and the retro-acceptance of electron density by the union is achieved using p-orbitals of union. Such dienes not referred to as being p-linked. It will be understood that the present complexes can be formed and used as mixtures of the p-complexed and s-complexed diene compounds. The formation of the diene complex in either the p or s state depends on the choice of the diene, the specific metal complex and the reaction conditions employed in the preparation of the complex. Generally the terminally substituted dienes favor the formation of p-complexes and the internally substituted dienes favor the formation of s-complexes. Especially useful dienes for such complexes are the compounds that do not decompose under the reaction conditions used to prepare the complexes of the invention. Under conditions of subsequent polymerization, or in the formation of catalytic derivatives of the complexes present, the diene group may undergo chemical reactions or be replaced by another union. Examples of suitable dienes (two X or X 'groups taken together) include: butadiene, 1,3-pentadiene, 1,3-hexadiene, 2,4-hexadiene, 1,4-diphenyl-1,3-butadiene, 3 methyl-1,3-pentadiene, 1,4-dibenzyl-1,3-butadiene, 1-d-itolyl-1,3-butadiene, and 1,4-bis (trimethylsilyl) -1,3-butadiene. Examples of the preferred metal complexes according to the present invention include compounds wherein R "is methyl, ethyl, propyl, butyl, pentyl, hexyl, (including all isomers of the foregoing where applicable), cyclododecyl, norbornyl, benzyl , phenyl or a covalent bond to Q; Q is 1,2-ethylene or silane and the delocalized p-linked group is a cyclopentadienyl, tetramethylcyclopentadienyl, indenyl, tetrahydroindenyl, 2-methylindenyl, 2,3-dimethylindenyl, 2-methyl- 4-phenylindenyl, 3-N, N-dimethylamino-indenyl, 3- (pyrrolyl) inden-1-yl, 3- (pi rrol id i n i lo) inden-1-yl, fluoroenyl, tetrahydrofluoroenyl, indacenyl or octahydrofluoroenyl; M is titanium in the formal oxidation state +2 or +4; M 'is scandium in the formal oxidation state +3, titanium in the formal oxidation state +2, +3, or +4, or zirconium in the formal oxidation state +4. Examples of the foregoing metal complexes include all of the following (wherein the methyl groups are represented by the line segments and () n denotes a C1-20 hydrocarbylene linkage group): Even more preferred according to the invention are the bimetallic zirconium and titanium complexes corresponding to the formula: where: M independently of each occurrence is titanium or zirconium; R 'in each occurrence is hydrogen, hydrocarbyl, silyl, germyl, halo, cyano, halohydrocarbyl, hydrocarbyloxy, hydrocarbyloxy, di (hydrocarbylsilyl) amino, hydrocarbylsilyloamino, di (hydrocarbyl) amino, hydrocarbylene amino, di (hydrocarbyl) phosphino, hydrocarbyl sulfide, or hydrocarbyl hydrocarbyloxy substituted, said R 'having up to 20 non-hydrogen atoms, and optionally, two R' groups together form a divalent derivative thereof connected to adjacent cyclopentadienyl ring positions thereby forming a fused ring structure, Z independently of each occurrence is SiR * 2, CR * 2, SiR * 2SiR * 2, CR * 2 CR * 2, CR * = CR *, CR * 2 SiR * 2, or GeR * 2; wherein R * in each occurrence is independently hydrogen, hydrocarbyl, silyl, halogenated alkyl, or halogenated aryl, said R * having up to 12 non-hydrogen atoms; Y 'is -O-, -S-, -NR "-, or -PR, wherein R" is hydrogen, hydrocarbyl, silyl or silylohydrocarbyl of up to 12 non-hydrogen atoms, and X independently each occurrence is a group of ionic bond having up to 40 atoms exclusive of the class of bonds containing an aromatic p-system through which the group is attached to M, or optionally two X groups together form a conjugated or non-conjugated diene C4. 0 optionally substituted with one or more hydrocarbyl, silyl, halocarbyl, or halohydrocarbyl groups; and Q is a divalent anionic linking group having up to 20 atoms that are not hydrogen. Especially preferred metal coordination complexes correspond to the aforementioned formula II, wherein Q is a linear or cyclic hydrocarbylene or silane group of up to 20 non-hydrogen atoms; R 'is hydrogen, C-20 hydrocarbyl, or two adjacent R' groups together formed part of a fused ring system; X is chloride, NR "2, or R"; wherein R "is C? -10 hydrocarbyl, and Y'Z is: -R" - (ER "') m. wherein: E is independently each occurrence silicon or carbon; R" is C-i-io hydrocarbyl; R '"is C1-4alkyl, and m is an integer from 1 to 10. Even more preferred metal coordination complexes according to the present invention correspond to the aforementioned formula II, wherein M in both occurrences is titanium or zirconium Q is a 1, 2-ethanoyl, the unsaturated ring system is cyclopentadienyl or indenyl; X is chloride, N, N-dimethylamido or methyl; and Y'Z is: dimethyl (t-butylamido) silane. Examples of even more preferred bimetallic complexes above include: zirconium, di (N, N-dimethylamido) (N- (1,1-dimethyloethyl) -1 - ((1,2,3,3a, 7a -?) - 1H -inden-1-yl) -1,1-dimethylsilanaminate (2 -) - N) (3,3 '- (1,2-ethanediyl) bis-, zirconium, dimethyl (N- (1,1-dimethyl-ethyl) -1 - ((1,2,3,3a , 7a -?) - 1-inden-1-yl) -1,1-dimethylsilanaminate (2 -) - N) (3,3- (1,2-ethanediyl) bis-, titanium, di (N, N- dimethylamido) (N- (1,1-dimethyloethyl) -1 - ((2,3,3a, 7a -?) - H-inden-1-yl) -1,1-dimethylaminolane (2) -N) (3,3 '- (1, Petenediyl) bis-, or titanium, dimethyl (N- (1,1-dimethyloethyl) -1 - ((1, 2,3,3a, 7a -?) - 1 H-inden -1-yl) -1,1-dimethylsilanaminate (2 -) - N) (3,3 '- (1,2-ethanedienyl) bis. Such complexes are of the formula: wherein M is titanium or zirconium and X is methyl or dimethylolamido.

In general, the complexes of the present invention can be prepared by combining the diGrígnard or dimethalylated compound derived from the group Q in the resulting complex, with the precursor complex or mixture of complexes in a suitable non-interfering solvent at a temperature from -100 ° C to 300 ° C, preferably from -78 ° C to 130 ° C, more preferably from -10 to 120 ° C. More particularly, the complexes can be prepared by lithiating a compound of the formula HCp-Q-CpH, such as 1,2-ethane (bisinden-1-yl), by reacting the resulting dimetallic compound with the excess of dimethyl dichlorosilane, followed by 2 equivalents of t-butylamine, and reacting the resulting product with a salt of Zirconium or titanium tetrachloride. The corresponding diene or hydrocarbyl derivative can be prepared by the known exchange with the hydrocarbyl metal or conjugated diene under reducing conditions. Alternatively, the desired bimetal dihydrocarbyl complex can be formed directly by reaction with a tetramide of zirconium or titanium, especially titanium tetra (N-dimethylamide) or zirconium tetra (N, N-dimethylamide), under ring forming conditions, followed by the reaction with excess aluminum trialkyl to form the desired dialkyl derivative. Modifications of the aforementioned preparation process for preparing an alternative compound of the invention can be employed by that skilled in the art without departing from the scope of the present invention. Suitable reaction media for the formation of complexes are aromatic or aliphatic hydrocarbons and haiohydrocarbons, ethers and cyclic ethers. Examples include straight and branched chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; hydrocarbyl-substituted aromatic and aromatic compounds such as benzene, toluene, xylene, C1-4 dialkyl ethers, C ^ ether derivatives. dialkyl of (poly) alkylene glycols, and tetrahydrofuran. Mixtures of the above list of suitable solvents are also suitable. The recovery procedure involves the separation of the alkali metal or alkaline earth metal salt resulting and devolatilization of the reaction medium. If desired, extraction to a secondary solvent may be employed. Alternatively, if the desired product is an insoluble precipitate, filtration or other separation technique may be employed. The complexes are made catalytically active by combining with an activating cocatalyst or by using an activation technique. Activating cocatalysts suitable for use herein include polymeric or oligomeric alumoxanes, especially methylalumoxane, methyl aluminum alumoxylated triisobutyl aluminum, or diisobutyloalumoxane; strong Lewis acids (the term "strong" as used herein defines Lewis acids which are not Bronsted acids), such as compounds of the group 13 C? -30 hydrocarbyl substituted, especially tri (hydrocarbyl) aluminum- or tri ( hydrocarbyl) boron and its halogenated derivatives, having from 1 to 10 carbons in each hydrocarbyl or halogenated hydrocarbyl group, more especially perfluoronated tri (aryl) boron compounds, and more especially tris (pentafluorophenyl) borane or 1,4-tetrafluorophenylene bis (bis ( pentafluorophenyl) borane); non-coordinating, ionic compatible, non-polymeric activating compounds (including the use of such compounds under oxidizing conditions); and its combinations. The aforementioned activating cocatalysts and activation techniques have previously been taught with respect to different metal complexes in the following references: EP-A-277,003, US-A-5, 153, 157, US-A-5,064,802, US-A-5,321, 106, US-A-5,721,185, US-A-5,425,872, US-A-5,350,723, WO- 97-35893 (equivalent to USSN 08 / 818,530 filed March 14, 1997) and US provisional application 60/054586, filed September 15, 1997. Strong Lewis acid combinations, especially the combination of a trialkylaluminum compound having from 1 to 4 carbons in each alkyl group and a halogenated tri (hydrocarbyl) boron compound having from 1 to 10 carbons in each hydrocarbyl group, especially tris (pentafluorophenyl) borane; other combinations of such strong Lewis acid mixtures with an oligomeric or polymeric alumoxane; and combinations of a single strong Lewis acid, especially tri (pentafluorophenyl) borane with an oligomeric or polymeric alumoxane are especially desirable activating cocatalysts. The volumic electrolysis technique involves the electromechanical oxidation of the metal complex under electrolysis conditions in the presence of a supporting electrolyte comprising an inert, non-coordinating anion. In the art, solvents, supporting electrolytes and electrolytic potentials for electrolysis are used such that the electrolysis by-products that would render the catalytically inactive metal complex not formed substantially formed during the reaction. More particularly, suitable solvents are materials that are liquid under the conditions of electrolysis (generally from 0 to 1 00 ° C), able to dissolve the supporting electrolyte, and inert. "Inert solvents" are those that are not reduced or oxidized under the reaction conditions used for electrolysis. It is generally possible in view of the desired electrolysis reaction to choose a solvent and a supporting electrolyte which are not affected by the electrical potential used for the desired electrolysis. Preferred solvents include difluorobenzene (ortho, meta or para isomers), dimethoxyethane, and mixtures thereof. The electrolysis can be conducted in a standard electrolytic cell containing an anode and a cathode (also referred to as the electrode in operation and against electrode respectively). Suitable building materials for the cell are glass, plastic, ceramic and metal coated in metal. The electrodes are prepared from inert materials, through which conductive materials are used that are not affected by the reaction mixture or reaction conditions. Platinum or palladium are preferred inert conductive materials. Typically an ion permeable membrane such as a porous glass separates the cell into separate compartments, the functioning electrode compartment and a counter electrode compartment. The working electrode is immersed in a reaction medium comprising the metal complex to be activated support electrolyte, solvent and any other material desired to moderate the electrolysis or stabilize the resulting complex. The contra The electrode is immersed in a mixture of solvent and supporting electrolyte. The desired voltage can be determined by theoretical or experimental calculations by sweeping the cell using a reference electrode such as a silver electrode immersed in the electrolyte cell. The bottom cell current, the current tap in the absence of the desired electrolysis, is also determined. The electrolysis is completed when the current falls from the desired level to the background level. In this way, the complete conversion of 1 initial metal complex can be detected easily. The most suitable support electrolytes are salts comprising a cation and a non-coordinating, compatible anion, inert A. "The preferred support electrolytes are salts corresponding to the formula G + A " wherein: G + is a cation which is not reactive towards the starting and resulting complex; and A "is a non-coordinating compatible anion Examples of G + cations include phosphonium or tetrahydrocarbyl-substituted ammonium cations having up to 40 non-hydrogen atoms.A preferred cation is the tetra-n-butylammonium cation.

During the activation of the complexes of the present invention by volume electrolysis the cation of the supporting electrolyte for the counter electrode and A "migrates to the working electrode to become an anion of the resulting oxidized product.The solvent or the cation of the supporting electrolyte it is reduced in the counter electrode in equal molar quantity with the amount of oxidized metal complex formed in the working electrode Preferred support electrolytes are tetrakiscarbonoammonium salts of tetrakis (perfluoro-aryl) borates having from 1 to 10 carbons in each hydrocarbyl group, especially tetra-n-butyloammonium tetrakis (pentafluorophenyl) borate The suitable activator compounds useful as a cocatalyst in an embodiment of the present invention comprise a cation which is a Bronsted acid capable of donating a proton, and an anion A- not coordinating, compatible, inert The preferred anions are those containing a only coordination complex comprising a metal load bearing or metalloid core whose anion is capable of balancing the load of the active catalyst species (the metal cation) that is formed when two components are combined. Also, said anion will be sufficiently labile to be displaced by acetylenically unsaturated, olefinic and diolefinic compounds or other neutral Lewis bases such as ethers or nitriles. Suitable metals include, but are not limited to, aluminum, gold and platinum. Suitable metalloids include, but can not be found limited to, boron, phosphorus and silicon. Compounds containing anions comprising coordination complexes containing a single metal or metalloid atom are, of course, well known and many, particularly such compounds containing a single boron atom in the anion portion, are available commercially. Therefore, said single boron atom compounds are preferred. Preferably such cocatalysts can be represented by the following general formula: (L * -H) d + (Aa-) where L * is a Lewis neutral base; (L * -H) + is a Bronsted acid; Ad "is a non-coordinating compatible anion having a charge of d-, and D is an integer of 1 to 3. More preferably Ad" corresponds to the formula: [M'K + QV] < where: k is an integer from 1 to 3; n 'is an integer from 2 to 6; n'-k = d; M 'is an element selected from a group 13 of the Periodic Table of the Elements; and Q 'is independently of each occurrence a hydride, dialkyl amide, halide, alkoxide, aryloxide, hydrocarbyl or hydrocarbyl-haloalubstituted radical, said Q' having up to 20 carbons with the proviso that in no more than one occurrence Q 'is halide. In a more preferred embodiment, d is one, that is, the counter ion has a single negative charge and corresponds to formula A. The activating cocatalysts comprising boron which are particularly useful in the preparation of the catalysts of this invention may be represented by the following general formula: [L * -H] + [BQ "4] - where: L * is as defined, B is boron in a valence state of 3, and Q" is a fluorinated C? -2 or fluorinated group. More preferably, Q "is in each occurrence a fluorinated aryl group, especially a pentafluorophenyl group Illustrative but not limiting examples of boron compounds that can be used as an activating cocatalyst in the preparation of the improved catalysts of this invention are ammonium salts. tri-substituted such as: trimethylammonium tetrakis (pentafluoro ñilbo faith while, dimetiloanilinio tetrakis (pentafluoro ñilbo faith while, dimetilotetradeciloamonio tetrakis (pentafluorophenyl, dimetilohexadecilamonio tetrakis (pentafluorophenyl tetrakis dimetiooctadeciloamonio (pentafluorofe ñilbo time, metilobis (tetradecyl) ammonium tetrakis (pentafluorophenyl, metilobis (hexadecyl) quis ammonium tetra ( pentafluoro faith iodine, methylobis (octadecyl) ammonium tetrakis (pentafluorophenylborate, and mixtures thereof) Another suitable ion-forming activating cocatalyst comprises a salt of a cationic oxidizing agent and a non-coordinating compatible anion represented by the formula: (Oxe +) d (Ad ") e wherein: Oxe + is a cationic oxidizing agent having a charge of e +; e is an integer from 1 to 3; and Ad ", and d are as already described.Examples of cationic oxidizing agents include: ferrocenium, hydrocarbyl-substituted ferrocenium, Ag +, or Pb + 2. Preferred embodiments of Ad" are those anions previously defined with respect to Bronsted acid. containing activating cocatalysts, especially tetrakis (pentafluorophenyl) borate.

Another suitable ion-forming activating cocatalyst comprises a compound which is a carbenium ion salt and a compatible, non-coordinating anion represented by the formula: © + A " wherein: © + is a C1-20 carbenium ion; and A "is as defined above.A preferred carbenium ion is the triphenyl cation, that is triphenylcarbenium.The above-mentioned activating technique and the ion-forming cocatalysts are also preferably used in combination with a tri (hydrazoryl) aluminum compound having from 1 to 4 carbons in each hydrocarbyl group, a polymeric or oligomeric alumoxane compound, or a mixture of a tri (hydrocarbyl) aluminum compound having from 1 to 4 carbons in each hydrocarbyl group and an oligomeric or polymeric alumoxane The molar ratio of catalyst / The cocatalyst employed is preferably from 1: 10,000 to 100: 1, more preferably from 1: 5000 to 10: 1, more preferably from 1: 1000 to 1: 1. In a particularly preferred embodiment of the invention the cocatalyst can be used in combination with a compound of C3.30 trihydrocarbyl aluminum, a compound of C3.3o (hydrocarbyloxy) dihydrocarbyl aluminum, or polymeric or oligomeric alumoxane. Aluminum posts are used for their beneficial ability to clean impurities such as oxygen, water and aldehydes from the polymerization mixture. Preferred aluminum compounds include C2.6 trialkyl aluminum compounds, especially those wherein the alkyl groups are ethyl, propyl, isopropyl, n-butyl, isobutyl, pentyl, neopentyl, or isopentyl and methylalumoxane, modified methylalumoxane and diisobutyloalumoxane. The molar ratio of the aluminum compound to the metal complex is preferably from 1: to 10,000 to 1000: 1, more preferably from 1: 5000 to 100: 1, more preferably from 1: 100 to 100: 1. The catalysts may exist as cationic derivatives of the dual metal center complexes, such as the zwitterionic derivatives thereof, or in a relationship not yet determined with the cocatalyst activator. The catalysts can be used to polymerize ethylenically and / or acetylenically unsaturated monomers having from 2 to 20 carbon atoms either alone or in combination. Preferred monomers include the C1.20 alpha-olefins especially ethylene, propylene, isobutylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene and mixtures thereof. Other preferred monomers include vinylcyclohexene, vinylcyclohexane, styrene, C1-4 substituted alkyl styrene, tetrafluoroethylene, vinylbenzocyclobutane, ethylidene norbornene and 1,4-hexadiene. In general, polymerization can be achieved under conditions well known in the prior art for Ziegler-Natta or Kaminsky-Sinn type polymerization reactions, that is, temperatures from 0-250 ° C and pressures from atmospheric to 3000 atmospheres. If desired, you can use suspension, solution, milky paste, gas phase or high pressure, whether they are used in batch or continuous or under other process conditions. For example, the use of condensation in a gas phase polymerization is an especially desirable mode of operation for use of the present catalysts. Examples of such known polymerization processes are illustrated in WO 88/02009, US Pat. Nos. 5,084,534, 5,405,922, 4,588,790, 5,032,652, 4,543,399, 4,564,647, 4,522,987, and elsewhere, the teaching of which discloses conditions that can be employed with the polymerization catalysts of the present invention. A support, especially silica, alumina or a polymer (especially polytetrafluoroethylene or a polyolefin) can be employed and it is desirable to employ when the catalysts are used in a gas phase polymerization process with or without condensation. Methods for the preparation of support catalysts are disclosed in numerous references, examples of which are US Pat. Nos. 4,808,561, 4,912,075, 5,008,228, 4,914,253. and 5,086,025 and are suitable for the preparation of supported catalysts of the present invention. In most polymerization reactions the molar ratio of the catalyst: polymerizable compounds employed is from 10"12: 1 to 10" 1: 1, more preferably 10"12: 1 to 10-5: 1. Suitable solvents for solution , suspension, pasta Milky or high pressure polymerization processes are non-coordinating inert liquids. Examples include straight and branched chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane, and mixtures thereof; alicyclic and cyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; perfluorinated hydrocarbons such as perfluorinated C-10 alkanes, and substituted alkyl aromatic and aromatic compounds such as benzene, toluene and xylene. Suitable solvents also include liquid olefins which can act as a monomer or comonomers including ethylene, propylene, butadiene, cyclopentene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1,4-hexadiene, 1 -octene, 1 -decene, styrene, divinylbenzene, allylobenzene, and vinylotoluene (including all isomers alone or as a mixture), mixtures of the abovementioned are also suitable. Having described the invention, the following examples and illustrations are provided, which should not be considered as limiting thereof. Unless stated otherwise, all parts and percentages are expressed on the basis of weight. The invention disclosed herein may be performed in the absence of any reactor not specifically described. Tetrahydrofuran (THF), diethyl ether, toluene and hexane were used following a passage through double columns loaded with activated alumina and Q-5R catalyst. The compounds [1,3-bis (diphenyl-phosphino) propane] dichloron-nickel (ll), MgCH2Si (CH3) 3, n-Buli, and pentamethylenebis (magnesium bromide) were all used as purchased from Aldrich. 2-bromoindene was prepared by dehydration of 2-bromoindanol and its identity confirmed by comparison to literature. All the syntheses were carried out under dry nitrogen or argon atmospheres using a combination of glove box and high vacuum techniques.

Example 1 Titanium, dichloro (N- (1, 1-dimet i loeti lo) - ((1, 2, 3,3a, 7a -?) - 1 H-inden-1-yl) -1,1-dimethylsilanaminate (2- ) -N) (2,2 '- (1,5-pentanediyl) bis- Preparation of pentamethylenebis (inden-2-yl). 2-Bromoindene (22.26 g, 114.1 mmol) and [1,3-bis (diphenylphosphino) -propane] dichloroniquel (II) (0.523 g, 0965 mmol) in diethyl ether (159 mL) were stirred at -78 ° C as a solution of pentamethylenebis (magnesium bromide) (57.1 mmol, 114.1 ml, 0.5M solution in tetrahydrofuran (THF)) was slowly added. Then it was removed in a dry ice bath and the sample was allowed to warm slowly to about 20 ° C and then it remained two. more hours at room temperature. After the reaction period the sample was emptied onto ice and washed with 1M HCl (1 x 100 mL), 1M NaHCO3 (1 x 100 mL), and then H2O (1 X 100 mL). The organic fraction was then dried over MgSO 4, filtered and the volatiles were removed resulting in the isolation of a yellow oil. Recrystallization from methanol resulted in the isolation of the desired product as a white crystalline solid (7.23 g, 42.1 percent yield).

Preparation of pentamethylenebis (1 - ((t-butylamino) dimethylsilyl) inden-2-yl). Pentamethylenebis (inden-2-yl) (31001 g, 9.987 mmol) in THF (50 mL) was stirred as nBuLi (20.0 mmol, 10.00 mL of 2.0M solution in cyclohexane) was added slowly. This mixture was allowed to stir for 16 hours. This solution was then added dropwise to a solution of CISi (CH3) 2NH-t-Bu (3.501 g, 21.23 mmol) in THF (100 mL). This mixture was allowed to stir for 16 hours. After the reaction period the volatiles were removed under vacuum and the residue was extracted and filtered using toluene. Removal of toluene under vacuum resulted in the isolation of the desired product as a light yellow solid (4.827 g, 86.5 percent yield).

Preparation of tetralithium pentamethylenebis (1 - ((t-butylamino) dimethylsilyl) inden-2-yl) »4 THF pentamethylenebis (1 - ((t-butylamino) dimethylsilyl) inden-2-yl) (3.182 g, 5.69 mmol ) in THF (100 mL) as n BuLi (26.0 mmol, 13.00 mL of 2.0 M solution in cyclohexane) was added slowly. This mixture was then left stirring throughout the night. After the reaction period the volatiles were removed and the residue was washed well with hexane and dried under vacuum. The desired product was then isolated as a tan solid and used without further purification or analysis (4749 g, 97.1 percent yield).

Preparation of titanium, dichloro (N- (1,1-dimethyloethyl) -1 - ((1,2,3,3a, 7,7a -?) - 1 H -inden-1-yl) 1,1-dimethylsilanaminate (2 -) - N) (2, 2 '- (1,5-pentadienyl) bis- Tetralithium pentamethylenebis (1 - ((t-butylamino) dimethylsilyl) inden-2-yl) "4 THF (2.6647) was added dropwise. g, 3.081 mmol) in THF (50 mL) was added to a milky paste of TiCl 3 (THF) 3 (2,809 g, 7.5 80 mmol) in THF (100 mL) .This mixture was stirred for three hours, then PbCl 2 (2,254 g) was added. g, 8.104 mmol) as a solid and the mixture was stirred for an additional hour.After the reaction period the volatiles were removed under vacuum and the residue extracted and filtered using toluene.The toluene was then removed under vacuum and the residue lowered in vacuo. hexane / CH2CI2 (100mL / 25mL), filtered and dried under vacuum resulting in the isolation of the product desired as a red / brown microcrystalline solid (1186 g, 48.6 percent yield).

Example 2 Titanium, bis (trimethylsilylmethyl) (N- (1,1-dimethyloethyl) -1- ((1,2,3,3a, 7a -?) - 1 H -inden-1-yl) -1,1-dimethylsilanaminate (2) -) - N) (2,2 '- (1,5-pentanediyl) bis- X = CH2Si (CH3) 3 Titanium, dichloro (N- (1,1-dimethyloethyl) -1 - ((1, 2,3,3a, 7a -?) - 1 H -inden-1-yl) -1,1-dimethylsilanaminate (2-) -N) (2,2 '- (1,5-pentanediyl) bis - (0.934 g, 1.18 mmol) was stirred in diethyl ether (100 mL) as MgCH2SI (CH3) 3 (4.72 mmol, 4.72) was added dropwise. mL of 1M solution is THF.) This mixture was stirred overnight.After the reaction period the volatiles were removed under vacuum and the residue was extracted and filtered using hexane.Removal of hexane under vacuum resulted in the isolation of hexane. a solid gold (0.911 g, 77.3 percent of production).

Polymerization A two-liter reactor is charged with 750 g of Isopar E and 120 g of octene-1 comonomer. Hydrogen is added as a molecular weight control agent by differential pressure expansion from an additional 75 ml tank from 300 psig (2070 Kpa) to 275 psig (1890 Kpa). The reactor is heated to the polymerization temperature of 140 ° C and saturated with ethylene at 500 psig (3450 Kpa). The appropriate amount of catalyst and cocatalyst was previously mixed as 0.005 M solutions in toluene (approximately 4 μmol) in a glove box to give a 1: 1 molar ratio of catalyst and cocatalyst, and transferred to a catalyst addition and injected tank to the reactor. The polymerization conditions were maintained for 10 minutes with ethylene on demand. The resulting solution was removed from the reactor in a purged nitrogen collection vessel containing 100 ml of isopropyl alcohol and 20 ml of 10 percent by weight of a toluene solution of clogged antioxidant phenol (lrganox® 1010 from Ciba Geigy Corporation) and stabilizer phosphorus (Irgafos 168). The polymers formed are dried in a vacuum oven programmed with a maximum temperature of 120 ° C and a heating cycle of 20 hours. The results are shown in Table 1.

Ta bla 1 Cocat Complex Course RReenndd .. ((qg)) EEff..11 MMII22 DDeennssity3 Mw / Mn 1 Ex.1 MAO4 18.4 47 2.42 - 2 Ex.2 MAO5 13.0 68 2.73 - 3 Ex.2 FAB6 1100..66 2288 ..7700 ..888811 2.3 4 Ex.4 ATPFB7 99..00 2233 ..4455 .. 887799 2.1 1. efficiency Kg polymer / g Ti 2. melt index, dg / min, measured by a microfusion indexer 3. (g / cm3) 4. methylalumoxane 5. methylalumoxane previously mixed with metal complex 15 minutes before its addition to the reactor 6. tris (pentafluorophenyl) borane previously mixed with metal complex 20 minutes before its addition to the reactor 7. dimethyloanilinium tetrakis (pentafluorophenyl) borane previously mixed with metal complex 20 minutes before its addition to the reactor Example 3 Titanium, di (N, N-dimethylamido) (N- (1,1-dimethyloethyl) - ((1, 2,3,3a, 7a -?) - 1 H -inden-1-yl) -1,1-dimethylsilanaminate (2 -) - N) (3,3 '- (1,2-ethanediyl) bis- A) Synthesis of 1,2-Ethanobis. { 3,3 '- (dimethylchlorosilyl) inden-1-i I o} In a 250 ml flask, 1, 2-bis (indenyl) ethane (10 g 38.7 mmol) was dissolved in 150 ml, Dry THF and the stirring solution was cooled to -78 ° C. Then, 52.3 ml of n-butylolithium (1.6M in hexanes, 83.7 mmol) was added dropwise with a syringe. The solution was taken brown and allowed to warm slowly at room temperature overnight. The solution was then added to a solution of Me2SiCl2 (25 mL) in 100 mL of THF at -78 ° C and the resulting mixture was slowly warmed to room temperature. All volatiles were removed under vacuum and the product was extracted with pentane. An oily product was obtained after filtration and removal of pentane under vacuum. Yield, 15 g (87%). The products are two isomers [(MSS) vs (RS, SR)] in a ratio of 1: 1 and were used without further purification. An isomer that has a lower solubility in pentane was gradually precipitated by removing the pentane very slowly over a period of one month. The analytical and spectroscopic data are as follows: Isomer I: 1 H NMR (C6D6, 23 ° C): d 7.544 (d, 2 H, 3 JH-H = 8.0 Hz, Ind, C6H4), 7.372 (d, 2 H, 3 JH -H = 7.2 Hz, Ind, C6H4), 7.248 (dd, 2 H, 3JH-H = 7.2 Hz, Ind, C6H4), 7.174 (dd, 2 H, 3JH-H = 7.5 Hz, Ind, C6H4), 6.273 (s, 2 H, Ind, C5H2), 3482 (s, 2 H, Ind, C5H2 ), 2920 (br, s, 4 H, CH2CH2), 0.041 (s, .6 H, SiMe2), -0.017 (s, 6 H, SiMe2). 13C NMR (C6D6, 23 ° C): d 144.967 (s, Ind), 144.003 (s, Ind), 143.897 (s, Ind), 127.887 (d, 1JC-H = 165.5 Hz, Ind), 126.015 (dd, 1JC-H = 158.1 Hz, 2JC-H = 6.3 Hz, Ind), 124.897 (dd, 1JC-H = 158.1 Hz, 2JC-H = 6.9 Hz, Ind), 123.785 (dd, 1JC-H = 157.1 Hz, 2JC -H = 7.4 Hz, Ind), 119,675 (dd, 1JC-H = 157.1 Hz, 2JC-H = 8.0 Hz, Ind), 45,826 (dd, 1JC-H = 131.6 Hz, 2JC-H = 8.5 Hz, Ind) , 27.043 (t, 1JC-H = 128.3 Hz, CH2CH2), -0.244 (q, JC-H = 121.6 Hz. SiMe2), -0.342 (q, 1JC-H = 121.5 Hz, SiMe2). Isomer II: 1H NMR (C6D6, 23 ° C): d 7.534 (d, 2 H, Ind, CßH4), 7352 (d, 2 H, Ind, C6H4), 7.241 (dd, 2 H, 3JH-H = 7.5 Hz, Ind, C6H4), 7.168 (dd, 2 H, Ind, C6H4), 6.31 (s, 2 H, Ind, C5H2), 3.49 (s, 2 H, Ind, C5H2), 2.91 (br, s, 4 H, CH2CH2), 0.064 (s, 6 H, SiMe2), -0.014 (s, 6 H, SiMe2). 13C NMR (C6D6, 23 ° C): d 144.975 (s, Ind), 144.060 (s, Ind), 143.920 (s, Ind), 127.944 (d, 1JC-H = 165.5 Hz, Ind), 126.029 (dd, 1JC-H = 158.1 Hz, 2JC-H = 6.3 Hz, Ind), 124.903 (dd, 1JC-H = 158.1 Hz, 2JC-H = 6.9 Hz, Ind), 123.791 (dd, 1JC-H = 157.1 Hz, 2JC -H = 7.4 Hz, Ind), 119,695 (dd, 1JC-H = 157.1 Hz, 2JC.H = 8.0 Hz, Ind), 45,868 (dd, 1JC-H = 130.6 Hz, 2JC-H = 8.4 Hz, Ind) , 27119 (t, 1JC-H 127.4 Hz, CH2CH2), -0.202 (q, 1JC-H = 122.1 Hz. SiMe2), -0.315 (q, 1JC-H = 122.1 Hz, SiMe2).

B) Synthesis of 1,2-ethanobis { 3,3 '- ((dimethyl) (t-butylamino) silyl) inden-1-yl} 1, 2-ethanobis { 3,3 '- (dimethylchlorosilyl) nden-1-yl} (15 g, 33.8 mmol) was dissolved with THF in a 250 mL flask and the stirring solution was cooled to 0 ° C. Bu'NH (16.3 mL, 154.8 mmol) was then added dropwise with a syringe. Immediately a white precipitate formed. The solution was stirred at room temperature overnight. Then all the volatiles were removed under vacuum and the product was extracted with pentane. An oily orange product was obtained after filtration and removal of pentane under vacuum. The products were two isomers [(RR.SS) vs (RS, SR)] in a ratio of 1: 1. The product was used to synthesize bimetallic complexes without further purification. Production, 14.2 g (91 percent). The spectroscopic and analytical data for the mixture are as follows: 1H NMR (C6D6, 23 ° C): d 7.636-7.231 (m, 16 H, Ind, C6H4), 6.496 (s, 2 H, Ind, C5H2), 6.461 (s, 2 H, Ind, C5H2), 3.477 (s, 4 H, Ind, C5H2), 3.165 (br, s, 8 H, CH2CH2), 1.067 (s, 32H, NCMe3), 0.491 (br, 4 H , NH), 0.002 (s, 6 H, SiMe2), -0.025 (s, 6 H, SiMe2), -0.054 (s, 12 H, SiMe2). 13C NMR (C6D6.23 ° C): d 146.830 (s, Ind), 145.507 (s, Ind), 145.464 (s, Ind), 142.297 (s, Ind), 142.199 (s, Ind), 131.093 (d, 1JC-H = 164.6 Hz, Ind), 125406 (dd, 1JC-H = 159.2 Hz, 2JC-H = 7.4 Hz, Ind), 124.376 (dd, 1 JC-H = 158.2 Hz, 2JC-H = 7.5 Hz, Ind), 123.900 (dd, 1JC-H = 155.0 Hz, 2JC-H = 6.4 Hz, Ind), 119.776 (dd, 1JC-H = 158.1 Hz, 2JC-H = 7.5 Hz, ind), 49.833 (s, NCMe3 ), 47,497 (dd, 1JC-H = 127.4 Hz, 2JC-H = 7.5 Hz, Ind), 34,195), 34,195 (t, 1JC-H = 128.3 Hz, NCMe3), 28,114 (t, 1JC-H = 127.9 Hz , CH2CH2), 27.946 (t, 1JC-H = 127.9 Hz, CH2CH2), 0.512 (q, 1JC.H = 118.9 Hz. S¡Me2), 0.456 (q, 1JC-H = 118.9 Hz, S¡Me2), -0.248 (q, 1JC-H = 118.9 Hz, SiMe2).

C) Titanium, di (N, N-dimethylamido) (N- (1,1-dimethyloethyl) -1 - ((1, 2, 3,3a, 7a -?) - 1 H -inden-1-yl) -1,1-dimethylsilanaminate (2 -) - N) (3,3 '- (1,2-ethanediyl) bis- was dissolved 1, 2 -ethanobis { 3,3 '- ((dimethyl) (t-butylamino) silyl) inden-1-yl) (5.76 g, 11.2 mmol) with 35 mL of pentane in a 250 mL flask. Then a solution of Ti (NMe2) (5.0 g, 22.3 mmol) in 100 ml of toluene was added. The mixture was refluxed at 110 ° C for 30 hours with a slow but constant N2 purge to remove HNMe3. The concentrated solution was then cooled to 0 ° C to produce red crystals. The product was purified by recrystallization from toluene and washing with pentane. Product 4.3 g (49%). The analytical and spectroscopic data for the product are as follows. 1H NMR (C6D6, 23 ° C): d 7.906 (d, 2 H, 3 JH-H = 8.7 Hz, Ind, C6H4), 7.585 (d, 2 H, 3 JH-H = 8.0 Hz, Ind, C6H4), 7.020 (dd, 2 H, 3JH = 7.6 Hz, 3JH-H = 7.0 Hz, Ind, C6H4), 6.905 (dd, 2 H, 3JH-H = 8.4 Hz, 3JH-H = 6.6 Hz, Ind, C6H4), 6.333 (s, 2 H, Ind, C5H), 3450-3364 (m, 4 H, CH2CH2), 3027 (s, 12 H, TiNMe2), 2350 (s, 12 H, TiNMe2), 1240 (s, 18 H, NCMe3), 0.852 (s, 6 H, SiMe2), 0.643 (s, 6 H, SiMe2). 13C NMR (C6D6, 23 ° C): d 133.471 (nd), 131.171 (ind), 126.160 (ind), 126.026 (ind), 124.240 (ind), 123.810 (ind), 122.021 (Ind), 121.571 (ind) ), 91,058 (ind), 60,428 (NCMe3), 49,526 (TiNMe2), 47,816 (TiNMe2), 34,204 (NCMe 3), 30,222 (CH 2 CH 2), 5,155 (SiMe 2), 2,998 (SiMe 2).

Anal. Cale, for C40H68N6Si2Ti2: C, 61.20; H, 8.73; N, 10.71. Found: C, 61.41; H, 8.60; N, 10.71.

Example 4 Titanium, dim ethyl (N- (1,1-dim eti loeti lo) - 1 - ((1,2, 3,3a, 7a -?) - 1 H-inden-1-yl) -1,1-dimethylsilanaminate (2 -) - N) (3,3 '- (1,2-ethanediyl) bis- Titanium, di (N, N-dimethylamido) (N- (1,1-dimethyloethyl) -1 - ((1,2,3,3a, 7a -?) - 1 H -inden-1-yl) -1 was dissolved , 1-dimethylsilanaminate (2 -) - N) 3,3'-1,2-ethanediyl) bis- (from Example 3) (800 mg, 1.02 mmol) with 100 mL toluene in a 250 mL flask. A solution of AIMe3 (5.0 mL, 2.0M in hexanes) was slowly added slowly with a syringe at room temperature. The solution was first taken yellow and then misty during the addition. The solution was stirred at room temperature for two days. All volatiles were removed by vacuum and the solid yellow product was purified by washing with pentane at room temperature. Product 607 mg (89%). The analytical and spectroscopic data for the product are as follows. 1H NMR (C6D6, 23 ° C): d 7.492 (d, 2H, 3JH-H = 8.7 Hz, Ind, C6H4), 7.463 (d, 2H, 3JH-H = 8.7 Hz, Ind, C6H4), 7.115 -7.066 (m, 2 H, Ind, C6H4), 6.928 (m, 2 H, Ind, C6H4), 5.997 (s, 2 H, Ind, C5H), 3.443-3.305 (m, 4 H, CH2CH2), 1457 (s, 18 H, NCMe3), 0.766 (s, 6 H, SiMe2), 0.569 (s, 6 H, SiMe2), 0.352 (s, 6 H, TiMe2), -0.111 (s, 6 H, TiMe2). 13C NMR (C6D6, 23 ° C): d 134.264 (ind), 132.596 (Ind), 127.782 (ind), 126.367 (ind), 126.072 (Ind), 125.755 (ind), 125.438 (ind), 124.073 (ind) , 90,165 (ind), 58,623 (NCMe3), 56,525 (TiMe2), 56,061 (TiMe2), 34,462 (NCMe3), 30,120 (CH2CH2), 4,010 (S¡Me2), 1,906 (SiMe2). Anal. Cale, for C36H56N2Si2Ti2: C, 64.65; H, 8.44; N, 4.19. Found: C, 63.65; H, 8.38; N, 4.10.

Example 5 Zirconium, di (N, N-dimethylamido) (N- (1,1-dimethyloethyl) - ((1, 2,3,3a, 7a -?) - 1 H -inden-1-yl) -1,1-dimethylsilanaminate (2 -) - N) (3,3 '- (1,2-ethanediyl) bis- 1,2-Ethanibis was dissolved. { 3,3 '- ((dimethyl) (t-butylamino) silyl) inden-1-yl} (5.0 g, 9.67 mmol) with 35 mL of pentane in a flask of 250 mL. Then a solution of Zr (NMe2) 4 (5.2 g, 10.4 mmol) in 100 mL of toluene was added. The mixture was refluxed at 110 ° C for 8 hours with a slow but constant purge of N2 to remove HNMe2. The concentrated solution was then cooled slowly to 0 ° C to produce light yellow crystals. The product was purified by recrystallization from toluene and washing with pentane. Product 5.6 g (66 percent) The analytical and spectroscopic data for the product are as follows: 1 H NMR (C6D6, 23 ° C): d 7.90-7.86 (m, 2 H, Ind, C6H4), 7.55-7.49 (m , 2 H, Ind, C6H4), 7.02-6.90 (m, 4 H, Ind, C6H4), 6.52 (s, 2 H, Ind, C5H), 6.50 (s, 2 H, Ind, C5H), 3.34 (br , s, 4 H, CH2CH2), 2.88 (s, 6 H, ZrNMe2), 2.87 (s, 6 H, ZrNMe2), 2.22 (s, 6 H, ZrNMe2), 2.21 (s, 6 H, ZrNMe2), 1.24 (s, 9 H, NCMe3), 1.23 (s, 9 H, NCMe3), 0.86 (s, 6 H, SiMe2), 0.67 (s, 6 H, SiMe2). 13C NMR (C6D6, 23 ° C): d 133.39 (ind), 129.46 (ind), 125.48 (ind), 124.05 (nd), 123.72 (ind), 123.70 (ind), 121.85 (ind), 121.79 (ind ), 121.58 (Ind), 121.43 (ind), 90.88 (Ind), 90.80 (ind), 56.38 (NCMe3), 44.57 (ZrNMe2), 44.53 (ZrNMe2), 42.39 (ZrNMe2), 34.58 (NCMe3), 29.58 (CH2CH2) ), 29.43 (CH2CH2), 5.85 (SiMe2), 3.51 (SiMe2). Anal. Cale, for C40H68N6Si2Zr2: C, 55.12; H, 7.86; N, 9.64. Found: C, 54.97; H, 7.91; N, 9.63.

Example 6 Zirconium, dimethyl (N- (1,1-dimethyloethyl) -1 - ((1, 2,3,3a, 7a -?) - 1 H- inden-1-yl) -1,1-dimethylsilanaminate (2-) -N) (1,3-2-ethanediyl) bis- Zirconium, di (N, N-dimethylamido) (N- (1,1-dimethyloethyl) -1 - ((1,2,3, 3a, 7a -?)) - 1 H -inden-1-yl) was dissolved. 1,1-dimethylsilanaminate (2 -) - N) (3,3 '- (1,2-ethanediyl) bis- (from Example 5) (800 mg, 0.92 mmol) with 100 mL toluene in a 250 mL flask. A solution of AIMe3 (5.0 mL, 2.0M in hexanes) was added slowly through a syringe at room temperature, the solution first turned yellow and then misty during the addition, the solution was stirred at room temperature for another 4 hours. volatile were removed under vacuum, and the solid white product was purified by washing with pentane at room temperature. Product 587 mg (84 percent). The analytical and spectroscopic data for the product are as follows: 1H NMR (C6D6, 23 ° C): d 7.594 (d, 2 H, 3JH-H = 8.7 Hz, Ind, C6H4), 7.362 (d, 2 H, 3JH -H = 7.2 Hz, Ind, C6H4), 7.028 (dd, 2 H, 3JH.H = 7.5 Hz, 3JH-H = 6.7 Hz, Ind, C6H4), 6.918 (dd, 2 H, 3JH-H = 8.4 Hz , 3JH.H = 6.7 Hz, Ind, C6H4), 6.259 (s, 2 H, Ind, C5H), 3.238 (br, s, 4 H, CH2CH2), 1,308 (s, 18 H, NCMe3), 0.621 (s , 6 H, SiMe2), 0.406 (s, 6 H, SiMe2), 0.181 (s, 6 H, ZrMe2), -0.715 (s, 6 H, ZrMe2). 13C NMR (C6D6, 23 ° C): d 133,644 (ind), 130,069 (nd), 126,072 (ind), 125,410 (nd), 125,157 (ind), 124,875 (Ind), 123,454 (nd), 122,961 (ind), 86. 726 (nd), 55,403 (NCMe3), 40,680 (ZrMe2), 39,160 (ZrMe2), 34,305 (NCMe3), 29,660 (CH2CH2), 4,473 (SiMe2), 2,665 (SiMe2). Anal. Cale, for C36H56N2Si2Zr2: C, 57.24; H, 7.47; N, 3.71. Found: C, 56.90; H, 7.43; N, 3.65.

Ethylene polymerization experiments In a high vacuum line (10"5 torr), ethylene polymerizations were carried out in 250 mL round bottom three-necked flasks equipped with a magnetic stir bar and a thermocouple probe. In a typical experiment, dry toluene (100 mL) was transferred in vacuum to the flask, previously saturated under 1.0 atm ethylene rigorously purified (pressure control using a continuous stream of mercury), and equilibrated at the desired reaction temperature using a bath The catalytically active species were generated again using a solution having a molar ratio metallocene: cocatalyst 1: 2 in 1.5 mnL of toluene.The catalyst solution was quickly injected into the flask rapidly stirred using a sealed syringe equipped with a spray needle The temperature of the toluene solution in representative polymerization experiments was controlled using a t ermopar (OMEGA Thermocouple Type K with a microprocessor thermometer Model HH2I). The increase in the exothermic reaction temperature was invariably less than 5 ° C during these polymerizations. After a measured time interval (short to minimize the Mass transport and exothermic effects), the polymerization was quenched by the addition of 15 mL 2% acidified methanol. Another 100 ml of methanol was then added and the polymer was collected by filtration, washed with methanol, and the high vacuum line dried overnight at a constant weight. Results are shown in table 2.

Table 2 Temp Time Complex Course ° C Cocat Prod. (G) Ef.1 Tm2 (° C) (nM) (min) 1 Ex.4 (0.1) 60 80 TCTPB3 23.5 2.4 _ 2 Ex.4 (0.1) 60 23 TCTPB4 0.27 0.03 - 3 Ex.2 (0.1) 4 90 BPFB5 0.85 1.3 134.1 4"3 FAB4 1.23 2.5 132.5 "30 100" 0.25 0.05 132.7 6"3 95« 0.35 0.53 133.4 1. efficiency Kg polymer / [(mol of metal complex) Atm h] 2. Polymer transition temperature of polymer 3. Trifenilopcarbeniotetraquís (pentafluorophenyl) borate Ph3C + [B (C6F5 ) 4] - 4. 1,4-tetrafluorophenylene-bis. {Bis (pentafluorophenyl) borane) ([1,4- (B (C6F5) 2) 2] ((C6F4)) 5. trispentafluorophenylborane

Claims (6)

1. A bimetallic complex according to claim 3 corresponding to the formula: R 'R' wherein: Q is a hydrocarbylene, linear or cyclic silane group, or a nitrogen or oxygen containing a derivative thereof, R 'is as already defined in claim 3, X and X' are C1-10 hydrocarbyl; and Y'Z * is -NR * - (ER '") m, where E is independent of each occurrence of silicon or carbon, R" is C ^ I O hydrocarbyl or a covalent bond to Q; R "" is C -? - alkyl, and m is an integer from 1 to 10.

2. A bimetallic complex according to claim 1 corresponding to the formula: where: M independently of each occurrence is titanium or zirconium; R 'in each occurrence is hydrogen, hydrocarbyl, silyl, germyl, halo, cyano, halohydrocarbyl, hydrocarbyloxy, hydrocarbyloxy, di (hydrocarbylsilyl) amino, hydrocarbylsilyloamino, di (hydrocarbyl) amino, hydrocarbylene amino, di (hydrocarbyl) phosphino, hydrocarbyl sulfide, or hydrocarbyl hydrocarbyloxy substituted, said R 'having up to 20 non-hydrogen atoms, and optionally, two R' groups together form a divalent derivative thereof connected to adjacent cyclopentadienyl ring positions thereby forming a fused ring structure, Z independently of each occurrence is SiR * 2, CR * 2, S * R * 2SiR * 2, CR * 2 CR * 2, CR * = CR *, CR * 2 SiR * 2, or GeR * 2; wherein R * in each occurrence is independently hydrogen, hydrocarbyl, silyl, halogenated alkyl, or halogenated aryl, said R * having up to 12 non-hydrogen atoms; Y 'is -O-, -S-, -NR "-, or -PR, wherein R" is hydrogen, hydrocarbyl, silyl or silylohydrocarbyl of up to 12 non-hydrogen atoms, and X independently each occurrence is an ionic bonding group having up to 40 atoms unique to the class of bonds containing an aromatic p-system through which the group is attached to M, or optionally two X groups together form a conjugated or non-conjugated diene C4.40 optionally substituted with one or more hydrocarbyl, silyl, halocarbyl, or halohydrocarbyl groups; and Q is a divalent anionic linking group having up to 20 non-hydrogen atoms.

3. A bimetallic complex according to claim 2 wherein: Q is a linear or cyclic hydrocarbylene or silane group of up to 20 non-hydrogen atoms; R 'is hydrogen, C? 20 hydrocarbyl, or two adjacent R' groups together formed part of a fused ring system; X is chloride, NR "2, or R"; wherein R "is C- | .10 hydrocarbyl, and Y'Z is: -NR" - (ER '") m. wherein: E is independently each occurrence of silicon or carbon, R" is C1-10 hydrocarbyl; R '"is Ct-4 alkyl, and M is an integer from 1 to 10.

4. A bimetallic complex according to claim 3 wherein: M in both occurrences is titanium or zirconium; Q is a 1,2-ethanediyl; the unsaturated ring system is cyclopentadienyl or indenyl; X is chloride, N, N-dimethylamido or methyl; and Y'Z is: dimethyl (t-butylamido) silane. A bimetallic complex according to claim 1 which is titanium, dichloro (N- (1,1-dimethyloethyl) -1 - ((1, 2,3,3a, 7a -?) - 1 H-inden-1 -yl) -1, 1-dimethylaminolane (2 -) - N) (2,2 '- (1,5-pentanodulph) b-s-, titanium, bis (trimethylsilylmethyl) (N- (1, 1-dimethyloethyl) -1 - ((1,2,3,3a, 7a -?) - 1 H -inden-1-yl) -1,1-dimethylsilanaminate (2 -) - N) (2,2 '- ( 1,5-pentanediyl) bis-, zirconium, di (N, N-dimethylamido) (N- (1,1-dimethyloethyl) -1 - ((1, 2, 3,3a, 7a -?) - 1H-inden -1-yl) -1,1-dimethylsilanaminate (2 -) - N) (2,2 '- (1,5-pentanediyl) bis-, zirconium, dimethyl (N- (1,1-dimethyloethyl) -1- ((1,2,3, 3a, 7a -?) - 1 H -inden-1-yl) -1,1-dimethylsilanaminate (2-) N) (2,2 '- (1,5-pentanediyl) bis- , titanium, di (N, N-dimethylamido) (N- (1,1-dimethyloethyl) -1 - ((1,2, 3,3a, 7a -?) - 1 H -inden-1-yl) -1, 1-dimethylsilanaminate (2 -) - N) (2, 2 '- (1,5-pentanediyl) bis-, or titanium, dimethyl (N- (1,1-dimethyloethyl) -1 - ((1,2,3 , 3a, 7a -?) - 1H-inden-1-yl) -1,1-dimethylsilanaminate (2 -) - N) (2,2 '- (1,5-pentanediyl) bis- 6. In a process for coordination d polymerization of polymerizable monomers whose improvement is that the catalyst comprises a bimetallic complex according to any of claims 1 to 5 and an activating cocatalyst.