DE19917984A1 - Chemical compound, process for its preparation and its use in a catalyst system for the production of polyolefins - Google Patents

Abstract

The invention relates to a chemical compound that is neutrally synthesized. The inventive compound can, in conjunction with an organometallic compound, form a novel catalyst system that can be advantageously used for polymerizing olefins. According to the invention, it is possible to attain a high degree of catalyst activity while forgoing the use of aluminum oxane, such as methyl aluminum oxane (MAO), as a cocatalyst.

Description

The present invention describes a chemical compound which is neutral is constructed. In combination with an organometallic compound, this can be a Form new catalyst system, which is advantageous for the polymerization of olefins is used. Here, the use of aluminum oxane such as Methyl aluminum oxane (MAO) can be dispensed with as a cocatalyst and still be a high catalyst activity can be achieved.

The role of cationic complexes in Ziegler-Natta polymerization Metallocenes are generally recognized (H. H. Brintzinger, D. Fischer, R. Mülhaupt, R. Rieger, R. Waymouth, Angew. Chem. 1995, 107, 1255-1283).

MAO as the most effective cocatalyst to date has the disadvantage of being in a large excess to be used, which leads to a high unwanted aluminum content in the Polymer leads. The representation of cationic alkyl complexes opens the way to MAO free catalysts with comparable activity, the co-catalyst almost can be used stoichiometrically.

The synthesis of "cation-like" metallocene polymerization catalysts is described in J. Am. Chem. Soc. 1991, 113, 3623. The alkyl abstraction from a metallocene alkyl compound takes place therein using trispentafluorophenylborane. EP-A-0 427 697 describes this synthetic principle and a corresponding catalyst system consisting of a neutral metallocene species (e.g. Cp ₂ ZrMe ₂ ), a Lewis acid (e.g. B (C ₆ F ₅ ) ₃ ) and aluminum alkyl claimed. A process for the preparation of salts of the general form LMX ⁺ XA ^- according to the principle described above is disclosed in EP-A-0 520 732.

Disadvantages of the existing alternative co-catalyst systems are their high ones Sensitivity to catalyst poisons and the problem of "leaching" at the Support of the catalyst systems.

So the task was a chemical compound with less Finding a tendency to coordinate, which has the disadvantages of the prior art avoids and still enables high polymerization activities.

The present invention thus relates to a chemical compound, a method for their production and their use in catalyst system for production of polyolefins. It also relates to a catalyst system containing at least a chemical compound according to the invention as a cocatalyst.

The chemical compound according to the invention corresponds to the general formula (I)

[(R ¹ ) -XM ¹ (R ³ ) -X- (R ² )] _k (I)

wherein
R ¹ , R ^{2 are the} same or different and are a hydrogen atom, a halogen atom, a boron-free C ₁ -C ₄₀ carbon-containing group such as C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ haloalkyl, C ₁ -C ₁₀ alkoxy , C ₆ -C ₂₀ aryl, C ₆ -C ₂₀ haloaryl, C ₆ -C ₂₀ aryloxy, C ₇ -C ₄₀ arylalkyl, C ₇ -C ₄₀ haloarylalky, C ₇ -C ₄₀ alkylaryl, C ₇ -C ₄₀ - haloalkylaryl or an Si (R ⁴ ) ₃ group,
R ^{4 is} a boron-free C ₁ -C ₄₀ carbon-containing group such as C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ haloalkyl, C ₁ -C ₁₀ alkoxy, C ₆ -C ₂₀ aryl, C ₆ -C ₂₀ Haloaryl, C ₆ -C ₂₀ aryloxy, C ₇ -C ₄₀ arylalkyl, C ₇ -C ₄₀ haloarylalky, C ₁ -C ₄₀ alkylaryl, C ₇ -C ₄₀ - haloalkylaryl,
R ³ can be identical or different to R ¹ and R ² , a hydrogen atom, a halogen atom, a C ₁ -C ₄₀ carbon-containing group such as C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ haloalkyl, C ₁ -C ₁₀ -Alkoxy, C ₆ -C ₂₀ aryl, C ₆ -C ₂₀ haloaryl, C ₆ -C ₂₀ aryloxy, C ₇ -C ₄₀ arylalkyl, C ₇ -C ₄₀ haloarylalkyl, C ₇ -C ₄₀ alkylaryl , C ₇ -C ₄₀ - haloalkylaryl or an OSi (R ⁴ ) ₃ group,
X identically or differently denotes an element from group IV, V or VIa of the periodic table of the elements or an NH group,
M ^{1 is} an element of group IIIa of the periodic table of the elements and
k is a natural number from 1 to 100 and
The index k is the result of Lewis acid-base interactions of the chemical compound according to the invention, these mutually forming dimers, trimers or higher oligomers.

Compounds in which X is an oxygen atom or are particularly preferred is an NH group.

In addition, compounds in which M ^{1 is} aluminum or boron are particularly preferred.

R ¹ and R ² are particularly preferably a boron-free C ₁ -C ₄₀ hydrocarbon radical which can be halogenated, preferably perhalogenated, with halogen such as fluorine, chlorine, bromine or iodine, in particular a halogenated, in particular perhalogenated C ₁ -C ₃₀ alkyl group such as trifluoromethyl, pentachloroethyl, heptafluoroisopropyl or monofluoroisobutyl or a halogenated C ₆ -C ₃₀ aryl group such as pentafluorophenyl, 2,4,6-trifluorophenyl, heptachloronaphthyl, heptafluoronaphthyl, heptafluorotolyl, 3,5-bis (trifluoromethyl) -, 2,4,6-tris (trifluoromethyl) phenyl, nonafluorobiphenyl or 4- (trifluoromethyl) phenyl. Also preferred for R ¹ and R ² are radicals such as phenyl, naphthyl, anisyl, methyl, ethyl, isopropyl, butyl, tolyl, biphenyl or 2,3-dimethylphenyl. Particularly preferred for R ¹ and R ² are pentafluorophenyl, phenyl, biphenyl, bisphenylmethylene, 3,5-bis (trifluoromethyl) phenyl, 4- (trifluoromethyl) phenyl, nonafluorobiphenyl, bis (pentafluorophenyl) methylene and 4- Methylphenyl.

R ³ is particularly preferably a boron-free C ₁ -C ₄₀ hydrocarbon radical which can be halogenated, preferably perhalogenated, with halogen such as fluorine, chlorine, bromine or iodine, in particular a halogenated, in particular perhalogenated C ₁ -C ₃₀ alkyl group such as trifluoromethyl , Pentachloroethyl, heptafluoroisopropyl or monofluoroisobutyl or a halogenated C ₆ -C ₃₀ aryl group such as pentafluorophenyl, 2,4,6-trifluorophenyl, heptachloronaphthyl, heptafluoronaphthyl, heptafluorotolyl, 3,5-bis (trifluoromethyl) phenyl, 2 , 4,6-tris (trifluoromethyl) phenyl, nonafluorobiphenyl or 4- (trifluoromethyl) phenyl. Also preferred for R ³ are radicals such as phenyl, naphthyl, anisyl, methyl, ethyl, isopropyl, butyl, tolyl, biphenyl or 2,3-dimethylphenyl.

Particularly preferred for R ³ are methyl, ethyl, isopropyl, butyl, pentafluorophenyl, phenyl, biphenyl, bisphenylmethylene, 3,5-bis (trifluoromethyl) phenyl, 4- (trifluoromethyl) phenyl, nonafluorobiphenyl , Bis (penta fluorophenyl) methylene and 4-methylphenyl.

Non-limiting examples to illustrate the formula I (can also be non-fluorinated):

The compounds of the formula (I) according to the invention are prepared from organoaluminum or organoboron compounds of the formula (II).

(R ⁵ ) ₃ Y (II)

wherein
R ^{5 is} a hydrogen atom or a boron-free C ₁ -C ₄₀ carbon-containing group such as C ₁ -C ₂₀ alkyl, C ₆ -C ₂₀ aryl, C ₇ -C ₄₀ arylalkyl, C ₇ -C ₄₀ alkylaryl or halogen atom can
Y is boron or aluminum.

Nonlimiting examples of the preferred compounds of formula (II) are: trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trihexyl aluminum, trioctyl aluminum, tri-n-butyl aluminum, tri-n-propyl aluminum, triisoprenaluminium, aluminum trichloride, aluminum tribranidium boron boron trichloride, trimethyl boron trichloride, Boron tribromide, boron triiodide, pentafluorophenyldimethylborane and pentafluorophenyldimethylaluminium The compound of the formula (I) according to the invention is prepared by reacting the compound of the formula (II) with compounds of the formula (III).

(R ⁶ ) X (R ¹ R ² ) (III)

wherein,
R ¹ and R ^{2 have} the meaning described under formula (I),
X is an oxygen, sulfur or an NH group, preferably oxygen or an NH group,
R ^{6 is} hydrogen, C ₁ -C ₄₀ carbon-containing group or a p-toluenesulfonic acid radical.

Non-limiting examples of the compound of formula (III) are: Pentaflourophenol, phenol, bis (pentafluorophenyl) carbinol, bis (phenyl) carbinol, Pentafluoroaniline, tris (pentaflourophenyl) silanol, bis (nonafluorodiphenyl) carbinol, Tris (nonafluorodiphenyl) silanol, nonafluorodiphenyl1-ol, nonafluorodiphenyl1-amine, Tris (phenyl) silanol, 3,5 bis (trifluoromethyl) aniline, 3,5 bis (trifluoromethyl) phenol, bis (2, 3,4 trifluorophenyl) carbinol, bis (3,5 trifluoromethylphenyl) carbinol, 2,3,4, Trifluorophenol, 2,3,4, trifluoroaniline, tris (2,3,4 trifluorophenyl) silanol, 2,4,6 Trifluoroaniline, 2,4,6 trifluorophenol, tris (2,4,6 trifluorophenyl) silanol, 3.5 Difluorophenol, 3,5 difluoroaniline, bis (3,5-difluorophenyl) carbinol, bis (2,4,6 difluorophenyl) carbinol

The preparation of the compound of formula (I) according to the invention is as follows described in more detail: In step A) one or more compounds of formula (II) in one Reaction vessel submitted. The compounds can either be in a solvent be dissolved or suspended, or also be in substance. As a solvent serve aliphatic or aromatic hydrocarbons such as n-pentane, isopentane, n-hexane, n-heptane, cyclohexane, isododecane, n-octane, n-nonane, n-decane, Petreleomether, toluene, benzene, o-xylene, m-xylene, p-xylene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 1,2,5-trimethylbenzene, 1,3,5-trimethylbenzene, ethylbenzene, Propylbenzene u. s. w. as well as mixtures of these. One or more connections Formula (II) are presented at temperatures between -100 ° C and 300 ° C.  

Temperatures between -80 ° C and 200 ° C are preferred. Are particularly preferred Temperatures between -80 ° C and 40 ° C. The compound of formula (II) should be in liquid phase.

Then one or more compounds of the formula (III) are added. These can also be dissolved or suspended in a solvent but also exist in substance. They already serve as solvents above described, preferably the same solvent is used. The addition takes place over a period of 1 minute up to 96 hours. One is preferred Addition time from 10 minutes to 8 hours. The temperature of the template is included the addition between -100 ° C and 200 ° C. Temperatures between are preferred -80 ° C and 100 ° C. Temperatures between -80 ° C. and are particularly preferred 40 ° C. The temperature is chosen so that at least one reactant in liquid phase. Furthermore, the implementation at normal pressure carried out. Depending on the physical properties of the compounds of the formula (II) is cooled with an intensive cooler, which may be operated with refrigerants becomes.

The stoichiometric ratio between compounds of formula (II) and Compounds of formula (III) is between 1: 1000 and 1: 100. A is preferred stoichiometric ratio between compounds of formula (II) and Compounds of formula (III) between 1: 100 and 1: 1, is particularly preferred 1: 2.

The reaction temperature is between -100 ° C and 200 ° C. One is preferred Reaction temperature between -80 ° C and 150 ° C. One is particularly preferred Reaction temperature between -80 ° C and 40 ° C. At least one reaction partner is preferably in the liquid phase. The reaction time is dependent of the selected reaction temperature and the selected compounds of Formula (III) between 1 minute and up to 96 hours. One is preferred Response time from 10 minutes to 8 hours.  

The resulting compounds of the formula (I) can be obtained according to step B) known technologies such as B. distillation, recrystallization, extraction or Sublimation to be isolated.

The chemical compounds of formula (I) according to the invention can be used together with an organometallic transition compound as a catalyst system, which is also the subject of the present invention. As an organometallic compound z. B. Metallocene compounds used. This can e.g. B. be bridged or unbridged biscyclopentadienyl complexes, as described for example in EP-A-0 129 368, EP-A-0 561 479, EP-A-0 545 304 and EP-A-0 576 970, monocyclopentadienyl complexes, such as bridged Amidocyclopentadienyl complexes which are described for example in EP-A-0 416 815, polynuclear cyclopentadienyl complexes as described for example in EP-A-0 632 063, π-ligand-substituted tetrahydropentalenes such as for example described in EP-A-0 659 758 or π-ligand-substituted tetrahydroindenes as described for example in EP-A-0 661 300. Organometallic compounds can also be used in which the complexing ligand does not contain a cyclopentadienyl ligand. Examples of this are diamine complexes of III. And IV. Subgroup of the Periodic Table of the Elements, as z. B. DH McConville, et al, Macromolecules, 1996, 29, 5241 and DH McConville, et al, J. Am. Chem. Soc., 1996, 118, 10008. In addition, diimine complexes of subgroup VIII of the Periodic Table of the Elements (eg Ni ²⁺ or Pd ²⁺ complexes), as described by Brookhart et al, J. Am. Chem. Soc. 1995, 117, 6414 and, Brookhart et al, J. Am. Chem. Soc., 1996, 118, 267 are used. Furthermore, 2,6-bis (imino) pyridyl complexes of subgroup VIII of the Periodic Table of the Elements (eg Co ²⁺ or Fe ²⁺ complexes), as described in Brookhart et al, J. Am. Chem. Soc. 1998, 120, 4049 and Gibson et al, Chem. Commun. 1998, 849 are used. Metallocene compounds whose complexing ligand contains heterocycles can also be used. Examples of this are described in WO 98/22486.

Preferred metallocene compounds are unbridged or bridged compounds of the formula (IV),

wherein
M is a metal of III., IV., V. or VI. Subgroup of the periodic table of the elements, in particular Ti, Zr or Hf,
R ^{10 are the} same or different and are a hydrogen atom or Si (R ¹² ) ₃ , in which R ^{12 is the} same or different a hydrogen atom or a C ₁ -C ₄₀ carbon-containing group, preferably C ₁ -C ₂₀ alkyl, C ₁ -C ₁₀ fluoroalkyl, C ₁ -C ₁₀ alkoxy, C ₆ -C ₂₀ aryl, C ₆ -C ₁₀ fluoroaryl, C ₆ -C ₁₀ aryloxy, C ₂ -C ₁₀ alkenyl, C ₇ -C ₄₀ - Arylalkyl, C ₇ -C ₄₀ alkylaryl or C ₈ -C ₄₀ arylalkenyl, or R ^{10 is} a C ₁ -C ₃₀ carbon-containing group, preferably C ₁ -C ₂₅ alkyl, such as methyl, ethyl, tert-butyl, Cyclohexyl or octyl, C ₂ -C ₂₅ alkenyl, C ₃ -C ₁₅ alkylalkenyl, C ₆ -C ₂₄ aryl, C ₅ -C ₂₄ - heteroaryl, C ₇ -C ₃₀ arylalkyl, C ₇ -C ₃₀ - Is alkylaryl, fluorine-containing C ₁ -C ₂₅ alkyl, fluorine-containing C ₆ -C ₂₄ aryl, fluorine-containing C ₇ -C ₃₀ arylalkyl, fluorine-containing C ₇ -C ₃₀ alkylaryl or C ₁ -C ₁₂ alkoxy, or two or a plurality of radicals R ¹⁰ can be linked to one another such that the radicals R ¹⁰ and the atoms of the cyclopentadienyl ring connecting them form a C ₄ -C ₂₄ ring system, which in turn can be substituted,
R ^{11 are the} same or different and are a hydrogen atom or Si (R ¹² ) ₃ , wherein R ^{12 is the} same or different a hydrogen atom or a C ₁ -C ₄₀ carbon-containing group, preferably C ₁ -C ₂₀ alkyl, C ₁ -C _10- fluoroalkyl, C ₁ -C ₁₀ alkoxy, C ₆ -C ₁₄ aryl, C ₆ -C ₁₀ fluoroaryl, C ₆ -C ₁₀ aryloxy, C ₂ -C ₁₀ alkenyl, C ₇ -C ₄₀ - Arylalkyl, C ₇ -C ₄₀ alkylaryl or C ₈ -C ₄₀ arylalkenyl, or R ^{11 is} a C ₁ -C ₃₀ carbon-containing group, preferably C ₁ -C ₂₅ alkyl, such as methyl, ethyl, tert-butyl, Cyclohexyl or octyl, C ₂ -C ₂₅ alkenyl, C ₃ -C ₁₅ alkylalkenyl, C ₆ -C ₂₄ aryl, C ₅ -C ₂₄ - heteroaryl, C ₅ -C ₂₄ alkyl heteroaryl, C ₅ -C ₂₄ - alkylheteroaryl C ₇ -C ₃₀ arylalkyl, C ₇ - C ₃₀ -alkylaryl, fluorinated C ₁ -C ₂₅ -alkyl, fluorinated C ₆ -C ₂₄ -aryl, fluorinated C ₇ -C ₃₀ -arylalkyl, fluorinated C ₇ -C ₃₀ -Alkylaryl or C ₁ -C ₁₂ -alkoxy, or two or more radicals R ¹¹ can be connected to one another such that the radicals R ¹¹ and which they binding atoms of the cyclopentadienyl ring form a C ₄ -C ₂₄ ring system, which in turn can be substituted,
I is 5 for v = 0 and I is 4 for v = 1,
m is 5 for v = 0 and m is 4 for v = 1,
L ^{1 can be the} same or different and represent a hydrogen atom, a C ₁ -C ₁₀ hydrocarbon group such as C ₁ -C ₁₀ alkyl or C ₆ -C ₁₀ aryl, a halogen atom, or OR ¹⁶ , SR ¹⁶ , OSi (R ¹⁶ ) ₃ , Si (R ¹⁶ ) ₃ , P (R ¹⁶ ) ₂ or N (R ¹⁶ ) ₂ , in which R ^{16 is} a halogen atom, a C ₁ -C ₁₀ alkyl group, a halogenated C ₁ -C ₁₀ alkyl group, a C ₆ -C ₂₀ aryl group or a halogenated C ₆ -C ₂₀ aryl group, or L ¹ is a toluenesulfonyl, trifluoroacetyl, trifluoroacetoxyl, trifluoromethanesulfonyl, nonafluorobutanesulfonyl or 2,2,2-trifluoroethanesulfonyl group,
o is an integer from 1 to 4, preferably 2,
Z denotes a bridging structural element between the two cyclopentadienyl rings and v is 0 or 1.

Examples of Z are groups M ² R ¹³ R ¹⁴ , in which M ^{2 is} carbon, silicon, germanium or tin and R ¹³ and R ^14, identical or different, are a C ₁ -C ₂₀ -hydrocarbon-containing group such as C ₁ -C ₁₀ alkyl, C ₆ -C ₁₄ aryl or trimethylsilyl. Z is preferably CH ₂ , CH ₂ CH ₂ , CH (CH ₃ ) CH ₂ , CH (C ₄ H ₉ ) C (CH ₃ ) ₂ , C (CH ₃ ) ₂ , (CH ₃ ) ₂ Si, (CH ₃ ) ₂ Ge, (CH ₃ ) ₂ Sn, (C ₆ H ₅ ) ₂ Si, (C ₆ H ₅ ) (CH ₃ ) Si, (C ₆ H ₅ ) ₂ Ge, (C ₆ H ₅ ) ₂ Sn , (CH ₂ ) ₄ Si, CH ₂ Si (CH ₃ ) ₂ , oC ₆ H ₄ or 2,2 '- (C ₆ H ₄ ) ₂ . Z can also form a mono- or polycyclic ring system with one or more R ¹⁰ and / or R ¹¹ radicals.

Chiral bridged metallocene compounds of the formula (IV) are preferred, in particular those in which v is 1 and one or both cyclopentadienyl rings are substituted so that they represent an indenyl ring. The indenyl ring is preferably substituted, in particular in the 2-, 4-, 2,4,5-, 2,4,6-, 2,4,7 or 2,4,5,6-position, with C ₁ -C ₂₀ -carbon-containing groups, such as C ₁ -C ₁₀ alkyl or C ₆ - C ₂₀ aryl, where two or more substituents of the indenyl ring can together form a ring system.

Chiral bridged metallocene compounds of the formula (IV) can be used as pure racemic or pure meso compounds are used. But it can also Mixtures of a racemic compound and a meso compound be used.

Examples of metallocene compounds are:
Dimethylsilanediylbis (indenyl) zirconium dichloride
Dimethylsilandiylbis (4-naphthyl-indenyl) zirconium dichloride
Dimethylsilanediylbis (2-methyl-benzo-indenyl) zirconium dichloride
Dimethylsilanediylbis (2-methyl-indenyl) zirconium dichloride
Dimethylsilanediylbis (2-methyl-4- (1-naphthyl) indenyl) zirconium dichloride
Dimethylsilanediylbis (2-methyl-4- (2-naphthyl) indenyl) zirconium dichloride
Dimethylsilanediylbis (2-methyl-4-phenyl-indenyl) zirconium dichloride
Dimethylsilanediylbis (2-methyl-4-t-butyl-indenyl) zirconium dichloride
Dimethylsilanediylbis (2-methyl-4-isopropyl-indenyl) zirconium dichloride
Dimethylsilanediylbis (2-methyl-4-ethyl-indenyl) zirconium dichloride
Dimethylsilanediylbis (2-methyl-4- acenaphth-indenyl) zirconium dichloride
Dimethylsilanediylbis (2,4-dimethyl-indenyl) zirconium dichloride
Dimethylsilanediylbis (2-ethyl-indenyl) zirconium dichloride
Dimethylsilanediylbis (2-ethyl-4-ethyl-indenyl) zirconium dichloride
Dimethylsilanediylbis (2-ethyl-4-phenyl-indenyl) zirconium dichloride
Dimethylsilandiybis (2-methyl-4,5-benzo-indenyl) zirconium dichloride
Dimethylsilanediylbis (2-methyl-4,6-diisopropyl-indenyl) zirconium dichloride
Dimethylsilanediylbis (2-methyl-4,5 diisopropyl-indenyl) zirconium dichloride
Dimethylsilanediylbis (2,4,6-trimethyl-indenyl) zirconium dichloride
Dimethylsilanediylbis (2,5,6-trimethyl-indenyl) zirconium dichloride
Dimethylsilanediylbis (2,4,7-trimethyl-indenyl) zirconium dichloride
Dimethylsilanediylbis (2-methyl-5-isobutyl-indenyl) zirconium dichloride
Dimethylsilanediylbis (2-methyl-5-t-butyl-indenyl) zirconium dichloride
Methyl (phenyl) silanediylbis (2-methyl-4-phenyl-indenyl) zirconium dichloride
Methyl (phenyl) silanediylbis (2-methyl-4,6-diisopropyl-indenyl) zirconium dichloride
Methyl (phenyl) silanediylbis (2-methyl-4-isopropyl-indenyl) zirconium dichloride
Methyl (phenyl) silanediylbis (2-methyl-4,5-benzo-indenyl) zirconium dichloride
Methyl (phenyl) silanediylbis (2-methyl-4,5- (methylbenzo) indenyl) zirconium dichloride
Methyl (phenyl) silanediylbis (2-methyl-4,5- (tetramethylbenzo) -indenyl) zirconium dichloride
Methyl (phenyl) silanediylbis (2-methyl-4- acenaphth-indenyl) zirconium dichloride
Methyl (phenyl) silanediylbis (2-methyl-indenyl) zirconium dichloride
Methyl (phenyl) silanediylbis (2-methyl-5-isobutyl-indenyl) zirconium dichloride
1,2-ethanediylbis (2-methyl-4-phenyl-indenyl) zirconium dichloride
1,4-butanediylbis (2-methyl-4-phenyl-indenyl) zirconium dichloride
1,2-ethanediylbis (2-methyl-4,6 diisopropyl-indenyl) zirconium dichloride
1,4-butanediylbis (2-methyl-4-isopropyl-indenyl) zirconium dichloride
1,4-butanediylbis (2-methyl-4,5-benzo-indenyl) zirconium dichloride
1,2-ethanediylbis (2-methyl-4,5-benzo-indenyl) zirconium dichloride
1,2-ethanediylbis (2,4,7-trimethyl-indenyl) zirconium dichloride
1,2-ethanediylbis (2-methyl-indenyl) zirconium dichloride
1,4-butanediylbis (2-methyl-indenyl) zirconium dichloride
[4- (η ⁵ -cyclopentadienyl) -4,6,6-trimethyl- (η ⁵ -4,5-tetrahydropentalen)] - dichlorozirconium
[4- (η ⁵ -3'-trimethylsilylcyclopentadienyl) -4,6,6-trimethyl- (η ⁵ -4,5-tetrahydropentalen)] - dichlorozirconium
[4- (η ⁵ -3'-isopropyl-cyclopentadienyl) -4,6,6-trimethyl- (η ⁵ -4,5-tetrahydropentalen)] - dichlorozirconium
[4- (η ⁵ -cyclopentadienyl) -4,7,7-trimethyl- (η ⁵ -4,5,6,7-tetrahydroindenyl)] dichlorotitanium
[4- (η ⁵ -cyclopentadienyl) -4,7,7-trimethyl- (η ⁵ -4,5,6,7-tetrahydroindenyl)] dichlorozirconium
[4- (η ⁵ -cyclopentadienyl) -4,7,7-trimethyl- (η ⁵ -4,5,6,7-tetrahydroindenyl)] - dichlorohafnium
[4- (η ⁵ -3'-tert-butyl-cyclopentadienyl) -4,7,7-trimethyl- (η ⁵ -4,5,6,7-tetrahydroindenyl)] - dichlorotitanium
4- (η ⁵ -3'-isopropylcyclopentadienyl) -4,7,7-trimethyl- (η ⁵ -4,5,6,7-tetrahydroindenyl)] dichlorotitanium
4- (η ⁵ -3'-methylcyclopentadienyl) -4,7,7-trimethyl- (η ⁵ -4,5,6,7-tetrahydroindenyl)] - dichlorotitanium
4- (η ⁵ -3'-trimethylsilyl-cyclopentadienyl) -2-trimethylsilyl-4,7,7-trimethyl- (η ⁵ -4,5,6,7-tetrahydroindenyl)] dichlorotitanium
4- (η ⁵ -3'-tert-butyl-cyclopentadienyl) -4,7,7-trimethyl- (η ⁵ -4,5,6,7-tetrahydroindenyl)] - dichlorozirconium
(Tertbutylamido) - (tetramethyl-η ⁵ -cyclopentadienyl) -dimethylsilyl-dichlorotitanium
(Tertbutylamido) - (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyl-dichlorotitan dichlorotitan
(Methylamido) - (tetramethyl-η ⁵ -cyclopentadienyl) -dimethylsilyl-dichlorotitan
(Methylamido) - (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyl dichlorotitanium
(Tertbutylamido) - (2,4-dimethyl-2,4-pentadiene-1-yl) dimethylsilyl-dichlorotitanium
Bis (cyclopentadienyl) zirconium dichloride
Bis (n-butylcyclopentadienyl) zirconium dichloride
Bis (1,3-dimethylcyclopentadienyl) zirconium dichloride
Tetrachloro- [1- [bis (η ⁵ -1H-inden-1-ylidene) methylsilyl] -3-η ⁵ -cyclopenta-2,4-dien-1-ylidene) -3-η ⁵ -9H-fluorene-9 ylidene) butane] di-zirconium
Tetrachloro- [2- [bis (η ⁵ -2-methyl-1H-inden-1-ylidene) methoxysilyl] -5- (η ⁵ -2,3,4,5-tetramethylcyclopenta-2,4-diene-1- ylidene) -5- (η ⁵ -9H-fluoren-9-ylidene) hexane] di-zirconium
Tetrachloro- [1- [bis (η ⁵ -1H-inden-1-ylidene) methylsilyl] -6- (η ⁵ -cyclopenta-2,4-dien-1-ylidene) -6- (η ⁵ -9H-fluorene 9-ylidene) -3-oxaheptane] di-zirconium
Dimethylsilanediylbis (2-methyl-4- (tert-butyl-phenyl-indenyl) zirconium dichloride
Dimethylsilanediylbis (2-methyl-4- (4-methyl-phenyl-indenyl) zirconium dichloride
Dimethylsilanediylbis (2-methyl-4- (4-ethyl-phenyl-indenyl) zirconium dichloride
Dimethylsilanediylbis (2-methyl-4- (4- trifluoromethyl-phenyl-indenyl) zirconium dichloride
Dimethylsilanediylbis (2-methyl-4- (4-methoxy-phenyl-indenyl) zirconium dichloride
Dimethylsilanediylbis (2-ethyl-4- (4-tert-butyl-phenyl-indenyl) zirconium dichloride
Dimethylsilanediylbis (2-ethyl-4- (4-methyl-phenyl-indenyl) zirconium dichloride
Dimethylsilanediylbis (2-ethyl-4- (4-ethyl-phenyl-indenyl) zirconium dichloride
Dimethylsilanediylbis (2-ethyl-4- (4-trifluoromethyl-phenyl-indenyl) zirconium dichloride
Dimethylsilanediylbis (2-ethyl-4- (4-methoxy-phenyl-indenyl) zirconium dichloride
Dimethylsilanediylbis (2-methyl-4- (4-tert-butyl-phenyl-indenyl) zirconium dimethyl
Dimethylsilanediylbis (2-methyl-4- (4-methyl-phenyl-indenyl) zirconium dimethyl
Dimethylsilanediylbis (2-methyl-4- (4-ethyl-phenyl-indenyl) zirconium dimethyl
Dimethylsilanediylbis (2-methyl-4- (4-trifluoromethyl-phenyl-indenyl) zirconium dimethyl
Dimethylsilanediylbis (2-methyl-4- (4-methoxy-phenyl-indenyl) zirconium dimethyl
Dimethylsilanediylbis (2-ethyl-4- (4-tert-butyl-phenyl-indenyl) zirconium dimethyl
Dimethylsilanediylbis (2-ethyl-4- (4-methyl-phenyl-indenyl) zirconium dimethyl
Dimethylsilanediylbis (2-ethyl-4- (4-ethyl-phenyl-indenyl) zirkoniumdiethyl
Dimethylsilanediylbis (2-ethyl-4- (4-trifluoromethyl-phenyl-indenyl) zirconium dimethyl
Dimethylsilanediylbis (2-ethyl-4- (4-methoxy-phenyl-indenyl) zirconium dimethyl
Dimethylsilanediylbis (2-methyl-4- (4'-tert-butyl-phenyl) indenyl) zirconium dichloride
Dimethylsilanediylbis (2-methyl-4- (4'-tert-butyl-phenyl) -indenyl) hafnuimdichlorid
Dimethylsilanediylbis (2-methyl-4- (4'-tert-butyl-phenyl) indenyl) titanium dichloride
Dimethylsilanediylbis (2-methyl-4- (4'-methyl-phenyl) indenyl) zirconium dichloride
Dimethylsilanediylbis (2-methyl-4- (4'-n-propyl-phenyl) indenyl) zirconium dichloride
Dimethylsilanediylbis (2-methyl-4- (4'-n-butyl-phenyl) indenyl) zirconium dichloride
Dimethylsilanediylbis (2-methyl-4- (4'-hexyl-phenyl) -indenyl) zirconium dichloride
Dimethylsilanediylbis (2-methyl-4- (4'-sec-butyl-phenyl) indenyl) zirconium dichloride
Dimethylsilanediylbis (2-ethyl-4-phenyl) indenyl) zirconium dichloride
Dimethylsilanediylbis (2-ethyl-4- (4'-methyl-phenyl) indenyl) zirconium dichloride
Dimethylsilanediylbis (2-ethyl-4- (4'-ethyl-phenyl) indenyl) zirconium dichloride
Dimethylsilanediylbis (2-ethyl-4- (4'-n-propyl-phenyl) indenyl) zirconium dichloride
Dimethylsilanediylbis (2-ethyl-4- (4'-n-butyl-phenyl) indenyl) zirconium dichloride
Dimethylsilanediylbis (2-ethyl-4- (4'-hexyl-phenyl) -indenyl) zirconium dichloride
Dimethylsilanediylbis (2-ethyl-4- (4'-pentylphenyl) indenyl) zirconium dichloride
Dimethylsilanediylbis (2-ethyl-4- (4'cyclohexyl-phenyl) indenyl) zirconium dichloride
Dimethylsilanediylbis (2-ethyl-4- (4'-sec-butyl-phenyl) indenyl) zirconium dichloride
Dimethylsilanediylbis (2-ethyl-4- (4'-tert-butyl-phenyl) indenyl) zirconium dichloride
Dimethylsilanediylbis (2-n-propyl-4-phenyl) indenyl) zirconium dichloride
Dimethylsilanediylbis (2-n-propyl-4- (4'-methyl-phenyl) indenyl) zirconium dichloride
Dimethylsilanediylbis (2-n-propyl-4- (4'-ethyl-phenyl) indenyl) zirconium dichloride
Dimethylsilanediylbis (2-n-propyl-4- (4'-iso-propyl-phenyl) -indenyl) zirconium dichloride
Dimethylsilanediylbis (2-n-propyl-4- (4'-n-butyl-phenyl) indenyl) zirconium dichloride
Dimethylsilanediylbis (2-n-propyl-4- (4'-hexyl-phenyl) -indenyl) zirconium dichloride
Dimethylsilanediylbis (2-n-propyl-4- (4'-cyclohexyl-phenyl) indenyl) zirconium dichloride
Dimethylsilanediylbis (2-n-propyl-4- (4'-sec-butyl-phenyl) indenyl) zirconium dichloride
Dimethylsilanediylbis (2-n-propyl-4- (4'-tert-butyl-phenyl) indenyl) zirconium dichloride
Dimethylsilanediylbis (2-n-butyl-4-phenyl) indenyl) zirconium dichloride
Dimethylsilanediylbis (2-n-butyl-4- (4'-methyl-phenyl) indenyl) zirconium dichloride
Dimethylsilanediylbis (2-n-butyl-4- (4'-ethyl-phenyl) indenyl) zirconium dichloride
Dimethylsilanediylbis (2-n-butyl-4- (4'-n-propyl-phenyl) indenyl) zirconium dichloride
Dimethylsilanediylbis (2-n-butyl-4- (4'-iso-propyl-phenyl) -indenyl) zirconium dichloride
Dimethylsilanediylbis (2-n-butyl-4- (4'-n-butyl-phenyl) indenyl) zirconium dichloride
Dimethylsilanediylbis (2-n-butyl-4- (4'-hexyl-phenyl) -indenyl) zirconium dichloride
Dimethylsilanediylbis (2-n-butyl-4- (4'-cyclohexyl-phenyl) indenyl) zirconium dichloride
Dimethylsilanediylbis (2-n-butyl-4- {4'-sec-butyl-phenyl) indenyl) zirconium dichloride
Dimethylsilanediylbis (2-n-butyltin 4- (4'-tert-butylphenyl) indenyl) zirconium dichloride
Dimethylsilanediylbis (2-hexyl-4-phenyl) indenyl) zirconium dichloride
Dimethylsilanediylbis (2-hexyl-4- (4'-methyl-phenyl) indenyl) zirconium dichloride
Dimethylsilanediylbis (2-hexyl-4- (4'-ethyl-phenyl) indenyl) zirconium dichloride
Dimethylsilanediylbis (2-hexyl-4- (4'-n-propyl-phenyl) indenyl) zirconium dichloride
Dimethylsilanediylbis (2-hexyl-4- (4'-iso-propyl-phenyl) -indenyl) zirconium dichloride
Dimethylsilanediylbis (2-hexyl-4- (4'-n-butyl-phenyl) indenyl) zirconium dichloride
Dimethylsilanediylbis (2-hexyl-4- (4'-hexyl-phenyl) -indenyl) zirconium dichloride
Dimethylsilanediylbis (2-hexyl-4- (4'-cyclohexyl-phenyl) indenyl) zirconium dichloride
Dimethylsilanediylbis (2-hexyl (4'-sec-butyl-phenyl) indenyl) zirconium dichloride
Dimethylsilanediylbis (2-hexyl-4- (4'-tert-butyl-phenyl) indenyl) zirconium dichloride
Dimethylsilanediylbis (2-methyl-4- (4'-tert-butylphenyl) indenyl) zirconium bis (dimethylamide)
Dimethylsilanediylbis (2-ethyl-4- (4'-tert-butylphenyl) indenyl) zirconium dibenzyl
Dimethylsilanediylbis (2-methyl-4- (4'-tert-butyl-phenyl) indenyl) zirconium dimethyl
Dimethylgermandiylbis (2-ethyl-4- (4'-tert-butyl-phenyl) indenyl) zirconium dichloride
Dimethylgermandiylbis (2-ethyl-4- (4'-tert-butyl-phenyl) -indenyl) hafniumdichiorid
Dimethylgermandiylbis (2-propyl-4- (4'-tert-butyl-phenyl) indenyl) titanium dichloride
Dimethylgermandiylbis (2-methyl-4- (4'-tert-butyl-phenyl) indenyl) zirconium dichloride
Ethylidenebis (2-ethyl-4-phenyl) indenyl) zirconium dichloride
Ethylidenebis (2-ethyl-4- (4'-tert-butyl-phenyl) indenyl) zirconium dichloride
Ethylidenebis (2-n-propyl-4- (4'-tert-butyl-phenyl) indenyl) zirconium dichloride
Ethylidenebis (2-n-butyl-4- (4'-tert-butyl-phenyl) indenyl) titanium dichloride
Ethylidenebis (2-hexyl-4- (4'-tert-butyl-phenyl) indenyl) zirconium dibenzyl
Ethylidenebis (2-ethyl-4- (4'-tert-butyl-phenyl) -indenyl) hafniumdibenzyl
Ethylidenebis (2-methyl-4- (4'-tert-butyl-phenyl) indenyl) titanium dibenzyl
Ethylidenebis (2-methyl-4- (4'-tert-butyl-phenyl) indenyl) zirconium dichloride
Ethylidenebis (2-ethyl-4- (4'-tert-butyl-phenyl) -indenyl) hafnium
Ethylidenebis (2-n-propyl-4 - phenyl) indenyl) titanium
Ethylidenebis (2-ethyl-4- (4'-tert-butyl-phenyl) -indenyl) zirconiumbis (dimethylamide)
Ethylidenebis (2-ethyl-4- (4'-tert-butyl-phenyl) -indenyl) hafniumbis (dimethylamide)
Ethylidenebis (2-ethyl-4- (4'-tert-butyl-phenyl) indenyl) titanium bis (dimethylamide)
Methylethylidenbis (2-ethyl-4- (4'-tert-butyl-phenyl) indenyl) zirconium dichloride
Methylethylidenbis (2-ethyl-4- (4'-tert-butyl-phenyl) indenyl) hafnium dichloride
Phenylphosphandiyl (2-ethyl-4- (4'-tert-butyl-phenyl) indenyl) zirconium dichloride
Phenylphosphandiyl (2-methyl-4- (4'-tert-butyl-phenyl) indenyl) zirconium dichloride
Phenylphosphandiyl (2-ethyl-4- (4'-tert-butyl-phenyl) indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-azapentalen) (2-methyl-4- (4'-methylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-5-azapentalen) (2-methyl-4- (4'-methylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-6-azapentalen) (2-methyl-4- (4'-methylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- (4'-methylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4- (4'-methylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-N-phenyl-6-azapentalen) (2-methyl-4- (4'-methylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-4-azapentalen) (2-methyl-4- (4'-methylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-6-azapentalen) (2-methyl-4- (4'-methylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-N-phenyl-4-azapentalen) (2-methyl-4- (4'-methylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-N-phenyl-6-azapentalen) (2-methyl-4- (4'-methylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-thiapentalen) (2-methyl-4- (4'-methylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-5-thiapentalen) (2-methyl-4- (4'-methylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-6-thiapentalen) (2-methyl-4- (4'-methylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-4-thiapentalen) (2-methyl-4- (4'-methylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-6-thiapentalen) (2-methyl-4- (4'-methylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-oxapentalen) (2-methyl-4- (4'-methylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-5-oxapentalen) (2-methyl-4- (4'-methylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-6-oxapentalen) (2-methyl-4- (4'-methylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-4-oxapentalen) (2-methyl-4- (4'-methylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-6-oxapentalen) (2-methyl-4- (4'-methylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-azapentalen) (2-methyl-4- (4'-ethylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-5-azapentalen) (2-methyl-4- (4'-ethylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-6-azapentalen) (2-methyl-4- (4'-ethylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- (4'-ethylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4- (4'-ethylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-N-phenyl-6-azapentalen) (2-methyl-4- (4'-ethylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-4-azapentalen) (2-methyl-4- (4'-ethylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-6-azapentalen) (2-methyl-4- (4'-ethylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-N-phenyl-4-azapentalen) (2-methyl-4- (4'-ethylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-N-phenyl-6-azapentalen) (2-methyl-4- (4'-ethylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-thiapentalen) (2-methyl-4- (4'-ethylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-5-thiapentalen) (2-methyl-4- (4'-ethylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-6-thiapentalen) (2-methyl-4- (4'-ethylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-4-thiapentalen) (2-methyl-4- (4'-ethylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-6-thiapentalen) (2-methyl-4- (4'-ethylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-oxapentalen) (2-methyl-4- (4'-ethylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-5-oxapentalen) (2-methyl-4- (4'-ethylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-6-oxapentalen) (2-methyl-4- (4'-ethylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-4-oxapentalen) (2-methyl-4- (4'-ethylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-6-oxapentalen) (2-methyl-4- (4'-ethylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-azapentalen) (2-methyl-4- (4'-n-propylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-5-azapentalen) (2-methyl-4- (4'-n-propylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-6-azapentalen) (2-methyl-4- (4'-n-propylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- (4'-n-propylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4- (4'-n-propylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-N-phenyl-6-azapentalen) (2-methyl-4- (4'-n-propylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-4-azapentalen) (2-methyl-4- (4'-n-propylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-6-azapentalen) (2-methyl-4- (4'-n-propylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-N-phenyl-4-azapentalen) (2-methyl-4- (4'-n-propylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-N-phenyl-6-azapentalen) (2-methyl-4- (4'-n-propylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-thiapentalen) (2-methyl-4- (4'-n-propylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-5-thiapentalen) (2-methyl-4- (4'-n-propylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-6-thiapentalen) (2-methyl-4- (4'-n-propylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-4-thiapentalen) (2-methyl-4- (4'-n-propylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-6-thiapentalen) (2-methyl-4- (4'-n-propylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-oxapentalen) (2-methyl-4- (4'-n-propylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-5-oxapentalen) (2-methyl-4- (4'-n-propylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-6-oxapentalen) (2-methyl-4- (4'-n-propylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-4-oxapentalen) (2-methyl-4- (4'-n-propylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-6-oxapentalen) (2-methyl-4- (4'-n-propylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-azapentalen) (2-methyl-4- (4'-isopropylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-5-azapentalen) (2-methyl-4- (4'-isopropylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-6-azapentalen) (2-methyl-4- (4'-isopropylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- (4'-isopropylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4- (4'-isopropylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-N-phenyl-6-azapentalen) (2-methyl-4- (4'-isopropylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-4-azapentalen) (2-methyl-4- (4'-isopropylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-6-azapentalen) (2-methyl-4- (4'-isopropylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-N-phenyl-4-azapentalen) (2-methyl-4- (4'-isopropylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-N-phenyl-6-azapentalen) (2-methyl-4- (4-isopropylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-thiapentalen) (2-methyl-4- (4'-isopropylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-5-thiapentalen) (2-methyl-4- (4'-isopropylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-6-thiapentalene) (2-methyl-4- (4'-isopropylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-4-thiapentalen) (2-methyl-4- (4'-isopropylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-6-thiapentalen) (2-methyl-4- (4'-isopropylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-oxapentalen) (2-methyl-4- (4'-isopropylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-5-oxapentalen) (2-methyl-4- (4'-isopropylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-6-oxapentalen) (2-methyl-4- (4'-isopropylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-4-oxapentalen) (2-methyl-4- (4'-isopropylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-6-oxapentalen) (2-methyl-4- (4'-isopropylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-azapentalen) (2-methyl-4- (4'-n-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-5-azapentalen) (2-methyl-4- (4'-n-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-6-azapentalen) (2-methyl-4- (4'-n-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- (4'-n-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4- (4'-n-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-N-phenyl-6-azapentalen) (2-methyl-4- (4'-n-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-4-azapentalen) (2-methyl-4- (4'-n-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-6-azapentalen) (2-methyl-4- (4'-n-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-N-phenyl-4-azapentalen) (2-methyl-4- (4'-n-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-N-phenyl-6-azapentalen) (2-methyl-4- (4'-n-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-thiapentalen) (2-methyl-4- (4'-n-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-5-thiapentalen) (2-methyl-4- (4'-n-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-6-thiapentalen) (2-methyl-4- (4'-n-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-4-thiapentalen) (2-methyl-4- (4'-n-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-6-thiapentalen) (2-methyl-4- (4'-n-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-oxapentalen) (2-methyl-4- (4'-n-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-5-oxapentalen) (2-methyl-4- (4'-n-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-6-oxapentalen) (2-methyl-4- (4'-n-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-4-oxapentalen) (2-methyl-4- (4'-n-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-6-oxapentalen) (2-methyl-4- (4'-n-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-azapentalen) (2-methyl-4- (4-s-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-5-azapentalen) (2-methyl-4- (4'-s-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-6-azapentalen) (2-methyl-4- (4'-s-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- (4'-s-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4- (4'-s-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-N-phenyl-6-azapentalen) (2-methyl-4- (4'-s-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-4-azapentalen) (2-methyl-4- (4'-s-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-6-azapentalen) (2-methyl-4- (4'-s-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-N-phenyl-4-azapentalen) (2-methyl-4- (4'-s-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-N-phenyl-6-azapentalen) (2-methyl-4- (4'-s-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-thiapentalen) (2-methyl-4- (4'-s-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-5-thiapentalen) (2-methyl-4- (4'-s-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-6-thiapentalen) (2-methyl-4- (4'-s-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-4-thiapentalen) (2-methyl-4- (4'-s-butylpheethyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-6-thiapentalene) (2-methyl-4- (4'-s-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-oxapentalen) (2-methyl-4- (4'-s-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-5-oxapentalen) (2-methyl-4- (4'-s-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-6-oxapentalen) (2-methyl-4- (4'-s-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-4-oxapentalen) (2-methyl-4- (4'-s-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-6-oxapentalen) (2-methyl-4- (4'-s-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-azapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-5-azapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-6-azapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-N-phenyl-6-azapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-4-azapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-6-azapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-N-phenyl-4-azapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-N-phenyl-6-azapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-thiapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-5-thiapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-6-thiapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-4-thiapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-6-thiapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-oxapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-5-oxapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-6-oxapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-4-oxapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-6-oxapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-azapentalen) (2-methyl-4- (4'-n-pentylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-5-azapentalen) (2-methyl-4- (4'-n-pentylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-6-azapentalen) (2-methyl-4- (4'-n-pentylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- (4'-n-pentylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4- (4'-n-pentylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-N-phenyl-6-azapentalen) (2-methyl-4- (4'-n-pentylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-4-azapentalen) (2-methyl-4- (4'-n-pentylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-6-azapentalen) (2-methyl-4- (4'-n-pentylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-N-phenyl-4-azapentalen) (2-methyl-4- (4'-n-pentylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-N-phenyl-6-azapentalen) (2-methyl-4- (4'-n-pentylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-thiapentalen) (2-methyl-4- (4'-n-pentylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-5-thiapentalen) (2-methyl-4- (4'-n-pentylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-6-thiapentalen) (2-methyl-4- (4'-n-pentylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-4-thiapentalen) (2-methyl-4- (4'-n-pentylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-6-thiapentalen) (2-methyl-4- (4'-n-pentylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-oxapentalen) (2-methyl-4- (4'-n-pentylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-5-oxapentalen) (2-methyl-4- (4'-n-pentylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-6-oxapentalen) (2-methyl-4- (4'-n-pentylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-4-oxapentalen) (2-methyl-4- (4'-n-pentylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-6-oxapentalen) (2-methyl-4- (4'-n-pentylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-azapentalen) (2-methyl-4- (4'-n-hexylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-5-azapentalen) (2-methyl-4- (4'-n-hexylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-6-azapentalen) (2-methyl-4- (4'-n-hexylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- (4'-n-hexylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4- (4'-n-hexylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-N-phenyl-6-azapentalen) (2-methyl-4- (4'-n-hexylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-4-azapentalen) (2-methyl-4- (4'-n-hexylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-6-azapentalen) (2-methyl-4- (4'-n-hexylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-N-phenyl-4-azapentalen) (2-methyl-4- (4'-n-hexylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-N-phenyl-6-azapentalen) (2-methyl-4- (4'-n-hexylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-thiapentalen) (2-methyl-4- (4'-n-hexylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-5-thiapentalen) (2-methyl-4- (4'-n-hexylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-6-thiapentalen) (2-methyl-4- (4'-n-hexylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-4-thiapentalen) (2-methyl-4- (4'-n-hexylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-6-thiapentalen) (2-methyl-4- (4'-n-hexylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-oxapentalen) (2-methyl-4- (4'-n-hexylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-5-oxapentalen) (2-methyl-4- (4'-n-hexylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-6-oxapentalen) (2-methyl-4- (4'-n-hexylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-4-oxapentalen) (2-methyl-4- (4'-n-hexylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-6-oxapentalen) (2-methyl-4- (4'-n-hexylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-azapentalen) (2-methyl-4- (4'-cyclohexylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyt-5-azapentalen) (2-methyl-4- (4 -cyclohexylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-6-azapentalen) (2-methyl-4- (4'-cyclohexylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- (4'-cyclohexylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4- (4'-cyclohexylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-N-phenyl-6-azapentalen) (2-methyl-4- (4'-cyclohexylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-4-azapentalen) (2-methyl-4- (4'-cyclohexylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-6-azapentalen) (2-methyl-4- (4'-cyclohexylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-N-phenyl-4-azapentalen) (2-methyl-4- (4'-cyclohexylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-N-phenyl-6-azapentalen) (2-methyl-4- (4'-cyclohexylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-thiapentalen) (2-methyl-4- (4'-cyclohexylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-5-thiapentalen) (2-methyl-4- (4'-cyclohexylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-6-thiapentalen) (2-methyl-4- (4'-cyclohexylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-4-thiapentalen) (2-methyl-4- (4'-cyclohexylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-6-thiapentalen) (2-methyl-4- (4'-cyclohexylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-oxapentalen) (2-methyl-4- (4'-cyclohexylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-5-oxapentalen) (2-methyl-4- (4'-cyclohexylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-6-oxapentalen) (2-methyl-4- (4'-cyclohexylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-4-oxapentalen) (2-methyl-4- (4'-cyclohexylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-6-oxapentalen) (2-methyl-4- (4'-cyclohexylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-azapentalen) (2-methyl-4- (4'-trimethylsilylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-5-azapentalen) (2-methyl-4- (4'-trimethylsilylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-6-azapentalen) (2-methyl-4- (4'-trimethylsilylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- (4'-trimethylsilylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4- (4'-trimethylsilylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-N-phenyl-6-azapentalen) (2-methyl-4- (4 'trimethylsilylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-4-azapentalen) (2-methyl-4- (4'-trimethylsilylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-6-azapentalen) (2-methyl-4- (4'-trimethylsilylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-N-phenyl-4-azapentalen) (2-methyl-4- (4 'trimethylsilylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-N-phenyl-6-azapentalen) (2-methyl-4- (4 'trimethylsilylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-thiapentalen) (2-methyl-4- (4'-trimethylsilylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-5-thiapentalen) (2-methyl-4- (4'-trimethylsilylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-6-thiapentalen) (2-methyl-4- (4'-trimethylsilylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-4-thiapentaene) (2-methyl-4- (4'-trimethylsilylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-6-thiapentalen) (2-methyl-4- (4'-trimethylsilylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-oxapentalen) (2-methyl-4- (4'-trimethylsilylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-5-oxapentalen) (2-methyl-4- (4'-trimethylsilylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-6-oxapentalen) (2-methyl-4- (4'-trimethylsilylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-4-oxapentalen) (2-methyl-4- (4'-trimethylsilylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-6-oxapentalen) (2-methyl-4- (4'-trimethylsilylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-azapentalen) (2-methyl-4- (4'-adamantylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-5-azapentalen) (2-methyl-4- (4'-adamantylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-6-azapentalen) (2-methyl-4- (4'-adamantylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- (4'-adamantylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4- (4'-adamantylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-N-phenyl-6-azapentalen) (2-methyl-4- (4'-adamantylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-4-azapentalen) (2-methyl-4- (4'-adamantylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-6-azapentalen) (2-methyl-4- (4'-adamantylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-4-azapentalen) (2-methyl-4- (4'-adamantylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-N-phenyl-4-azapentalen) (2-methyl-4- (4'-adamantylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-N-phenyl-6-azapentalen) (2-methyl-4- (4'-adamantylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-thiapentalen) (2-methyl-4- (4'-adamantylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-5-thiapentalen) (2-methyl-4- (4'-adamantylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-6-thiapentalen) (2-methyl-4- (4'-adamantylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-4-thiapentalen) (2-methyl-4- (4'-adamantylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-6-thiapentalen) (2-methyl-4- (4'-adamantylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-oxapentafen) (2-methyl-4- (4'-adamantylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-5-oxapentalen) (2-methyl-4- (4'-adamantylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-6-oxapentalen) (2-methyl-4- (4'-adamantylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-4-oxapentalen) (2-methyl-4- (4'-adamantylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-6-oxapentalen) (2-methyl-4- (4'-adamantylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-azapentalen) (2-methyl-4- (4'-tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-5-azapentalen) (2-methyl-4- (4'-tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-6-azapentalen) (2-methyl-4- (4'-tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4- (4'-tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4- (4'-tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-N-phenyl-6-azapentalen) (2-methyl-4- (4'-tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-4-azapentalen) (2-methyl-4- (4'-tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-6-azapentalen) (2-methyl-4- (4'-tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-N-phenyl-4-azapentalen) (2-methyl-4- (4'-tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-N-phenyl-6-azapentalen) (2-methyl-4- (4'-tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-thiapentalen) (2-methyl-4- (4'-tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-5-thiapentalen) (2-methyl-4- (4'-tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-6-thiapentalen) (2-methyl-4- (4'-tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-4-thiapentalen) (2-methyl- (4'-tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-6-thiapentalen) (2-methyl-4- (4'-tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-oxapentalen) (2-methyl-4- (4'-tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-5-oxapentalen) (2-methyl-4- (4'-tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-6-oxapentalen) (2-methyl-4- (4'-tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride Dimethylsilanediyl (2,5-dimethyl-4-oxapentalen) (2-methyl-4- ( 4'-tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-6-oxapentalen) (2-methyl-4- (4'-tris (trifluoromethyl) methylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-azapentalen) (2-ethyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-5,6-di-hydro-4-azapentalen) (2-ethyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-azapentalen) (2-ethyl-4- (4'-tert-butylphenyl-tetrahydroindenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-5-azapentalen) (2-n-butyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride
Ethylidene (2-methyl-6-azapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-N-trimethylsilyl-4-azapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-N-tolyl-5-azapentalen) (2-n-propyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride
Dimethylgermyldiyl (2-methyl-N-phenyl-6-azapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride
Methyl ethylidene (2,5-dimethyl-4-azapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-di-iso-propyl-6-azapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-N-phenyl-4-azapentalen) (2,6-dimethyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-N-phenyl-6-azapentalen) (2-methyl-4- (6'-tert-butylnaphthyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-N-phenyl-6-azapentalen) (2-methyl-4- (6'-tert-butylanthracenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-phosphapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride
Diphenylsilanediyl (2-methyl-5-thiapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride
Methylphenylsilanediyl (2-methyl-6-thiapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride
Methylidene (2,5-dimethyl-4-thiapentalene) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride
Dimethylmethylidene (2,5-dimethyl-6-thiapentalene) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride
Diphenylsilanediyl (2,5-dimethyl-4-oxapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride
Diphenylsilanediyl (2,5-dimethyl-6-oxapentalen) (2-methyl-4- (4'-tert-butylphenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-azapentalene) (2-methylindenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-5-azapentalene) (2-methylindenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-6-azapentalene) (2-methylindenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-N-phenyl-4-azapentalen) (2-methylindenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-N-phenyl-5-azapentalen) (2-methylindenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-N-phenyl-6-azapentalen) (2-methylindenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-4-azapentalene) (2-methylindenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-6-azapentalene) (2-methylindenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-N-phenyl-4-azapentalen) (2-methylindenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-N-phenyl-6-azapentalen) (2-methylindenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-thiapentalene) (2-methylindenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-5-thiapentalene) (2-methylindenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-6-thiapentalene) (2-methylindenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-4-thiapentalene) (2-methylindenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-6-thiapentalene) (2-methylindenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-oxapentalen) (2-methylindenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-5-oxapentalen) (2-methylindenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-6-oxapentalen) (2-methylindenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-4-oxapentalen) (2-methylindenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-6-oxapentalen) (2-methylindenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-azapentalene) (indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-5-azapentalene) (indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-6-azapentalene) (indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-N-phenyl-4-azapentalene) (indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-N-phenyl-5-azapentalene) (indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-N-phenyl-6-azapentalene) (indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-4-azapentalene) (indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-6-azapentalene) (indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-N-phenyl-4-azapentalene) (indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-N-phenyl-6-azapentalene) (indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-thiapentalene) (indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-5-thiapentalene) (indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-6-thiapentalene) (indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-4-thiapentalene) (indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-6-thiapentalene) (indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-oxapentalen) (indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-5-oxapentalen) (indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-6-oxapentalen) (indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-4-oxapentalen) (indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-6-oxapentalen) (indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-azapentalen) (2-methyl-4-phenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-5-azapentalen) (2-methyl-4-phenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-6-azapentalen) (2-methyl-4-phenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4-phenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4-phenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-N-phenyl-6-azapentalen) (2-methyl-4-phenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-4-azapentalen) (2-methyl-4-phenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-6-azapentalen) (2-methyl-4-phenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-N-phenyl-4-azapentalen) (2-methyl-4-phenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-N-phenyl-6-azapentalen) (2-methyl-4-phenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-thiapentalen) (2-methyl-4-phenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-5-thiapentalen) (2-methyl-4-phenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-6-thiapentalen) (2-methyl-4-phenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-4-thiapentalen) (2-methyl-4-phenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-6-thiapentalen) (2-methyl-4-phenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-oxapentalen) (2-methyl-4-phenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-5-oxapentalen) (2-methyl-4-phenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-6-oxapentalen) (2-methyl-4-phenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-4-oxapentalen) (2-methyl-4-phenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-6-oxapentalen) (2-methyl-4-phenyl-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-azapentalen) (2-methyl-4,5-benzo-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-5-azapentalen) (2-methyl-4,5-benzo-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-6-azapentalen) (2-methyl-4,5-benzo-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-N-phenyl-4-azapentalen) (2-methyl-4,5-benzo-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-N-phenyl-5-azapentalen) (2-methyl-4,5-benzo-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-N-phenyl-6-azapentalen) (2-methyl-4,5-benzo-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-4-azapentalen) (2-methyl-4,5-benzo-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-6-azapentalen) (2-methyl-4,5-benzo-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-N-phenyl-4-azapentalen) (2-methyl-4,5-benzo-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-N-phenyl-6-azapentalen) (2-methyl-4,5-benzo-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-thiapentalen) (2-methyl-4,5-benzoinidenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-5-thiapentalen) (2-methyl-4,5-benzoinidenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-6-thiapentalen) (2-methyl-4,5-benzoinidenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-4-thiapentalen) (2-methyl-4,5-benzo-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-6-thiapentalen) (2-methyl-4,5-benzo-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-4-oxapentalen) (2-methyl-4,5-benzo-indenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-5-oxapentalen) (2-methyl-4,5-benzoinidenyl) zirconium dichloride
Dimethylsilanediyl (2-methyl-6-oxapentalen) (2-methyl-4,5-benzo-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-4-oxapentalen) (2-methyl-4,5-benzo-indenyl) zirconium dichloride
Dimethylsilanediyl (2,5-dimethyl-6-oxapentalen) (2-methyl-4,5-benzo-indenyl) zirconium dichloride
Dimethylsilanediylbis (2-methyl-4-azapentalene) zirconium dichloride
Dimethylsilanediylbis (2-methyl-5-azapentalene) zirconium dichloride
Dimethylsilanediylbis (2-methyl-6-azapentalene) zirconium dichloride
Dimethylsilanediylbis (2-methyl-N-phenyl-4-azapentalene) zirconium dichloride
Dimethylsilanediylbis (2-methyl-N-phenyl-5-azapentalene) zirconium dichloride
Dimethylsilanediylbis (2-methyl-N-phenyl-6-azapentalene) zirconium dichloride
Dimethylsilanediylbis (2,5-dimethyl-4-azapentalene) zirconium dichloride
Dimethylsilanediylbis (2,5-dimethyl-6-azapentalene) zirconium dichloride
Dimethylsilanediylbis (2,5-dimethyl-N-phenyl-4-azapentalene) zirconium dichloride
Dimethylsilanediylbis (2,5-dimethyl-N-phenyl-6-azapentalene) zirconium dichloride
Dimethylsilanediylbis (2-methyl-4-thiapentalene) zirconium dichloride
Dimethylsilanediylbis (2-methyl-5-thiapentalene) zirconium dichloride
Dimethylsilanediylbis (2-methyl-6-thiapentalene) zirconium dichloride
Dimethylsilanediylbis (2,5-dimethyl-4-thiapentalene) zirconium dichloride
Dimethylsilanediylbis (2,5-dimethyl-6-thiapentalene) zirconium dichloride
Dimethylsilanediylbis (2-methyl-4-oxapentalen) zirconium dichloride
Dimethylsilanediylbis (2-methyl-5-oxapentalen) zirconium dichloride
Dimethylsilanediylbis (2-methyl-6-oxapentalen) zirconium dichloride
Dimethylsilanediylbis (2,5-dimethyl-4-oxapentalen) zirconiumdichloride
Dimethylsilanediylbis (2,5-dimethyl-6-oxapentalen) zirconium dichloride

Furthermore, the metallocenes in which the zirconium fragment "-zirconium dichloride" have the meanings
Zirconium monochloro-mono (2,4-di-tert-butyl-phenolate)
Zirconium monochloro-mono- (2,6-di-tert-butyl-phenolate)
Zirconium monochloro-mono (3,5-di-tert-butyl-phenolate)
Zirconium monochloro-mono- (2,6-di-sec-butyl-phenolate)
Zirconium monochloro-mono (2,4-di-methylphenoxide)
Zirconium monochloro-mono (2,3-di-methylphenoxide)
Zirconium monochloro-mono (2,5-di-methylphenoxide)
Zirconium monochloro-mono- (2,6-di-methylphenolate)
Zirconium monochloro-mono- (3,4-di-methylphenolate)
Zirconium monochloro-mono (3,5-di-methylphenoxide)
Zirconium monochloro-monophenolate
Zirconium monochloro-mono (2-methylphenoxide)
Zirconium monochloro-mono (3-methylphenoxide)
Zirconium monochloro-mono (4-methylphenoxide)
Zirconium monochloro-mono (2-ethylphenolat)
Zirconium monochforo-mono- (3-ethylphenolat)
Zirconium monochloro-mono (4-ethylphenolat)
Zirconium monochloro-mono (2-sec-butylphenoxide)
Zirconium monochloro-mono (2-tert-butylphenoxide)
Zirconium monochloro-mono (3-tert-butylphenoxide)
Zirconium monochloro-mono (4-sec-butylphenoxide)
Zirconium monochloro-mono (4-tert-butyiphenolat)
Zirconium monochloro-mono (2-isopropyl-5-methylphenoxide)
Zirconium monochloro-mono (4-isopropyl-3-methylphenoxide)
Zirconium monochloro-mono- (5-isopropyl-2-methylphenoxide)
Zirconium monochloro-mono- (5-isopropyl-3-methylphenoxide)
Zirconium monochloro-mono (2,4-bis (2-methyl-2-butyl) phenolate)
Zirconium monochloro-mono (2,6-di-tert-butyl-4-methylphenoxide)
Zirconium monochloro-mono (4-nonylphenolate)
Zirconium monochloro-mono (1-naphthoxide)
irkonium-monochloro-mono (2-naphtholate)
Zirconium monochloro-mono (2-phenylphenolate)
Zirconium monochloro mono- (tert.butoxide)
Zirconium monochloro-mono- (N-methylanilide)
Zirconium monochloro-mono (2-tert-butylanilid)
Zirconium monochloro-mono (tert-butylamide)
Zirconium monochloro-mono- (di-iso.-diisopropylamide)
Zirconium monochloro monomethyl
Zirconium monochloro-mono-benzyl
Zirconium monochloro mono neopentyl, has examples of the metallocenes according to the invention.

Also preferred are the corresponding zirconium dimethyl compounds, the corresponding zirconium- ^4- butadiene compounds, and the corresponding compounds with 1,2- (1-methyl-ethanediyl) -, 1,2- (1,1-dimethyl-ethanediyl) ) - and 1,2 (1,2-dimethyl-ethanediyl) bridge.

To produce the catalyst system according to the invention, one or several compounds of the formula (I) with an organometallic transition compound of the formula (IV) in any stoichiometric ratio.

The catalyst system according to the invention can additionally contain an aluminum compound of the formula (V)

contain.  

The radicals R ²⁰ in formula (V) can be identical or different and a halogen atom, a hydrogen atom, a C ₁ -C ₄₀ carbon-containing group, preferably C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ haloalkyl, C ₆ mean C ₄₀ arylalkyl, C ₇ -C ₄₀ -Halogenarylalkyl, C ₇ -C ₄₀ alkylaryl or C ₇ -C ₄₀ -haloalkylaryl - C ₂₀ aryl, C ₆ -C ₂₀ haloaryl, C. ₇

Preferred for R ²⁰ are C ₁ -C ₆ alkyl groups, particularly preferred for R ²⁰ are C ₁ -C ₄ alkyl groups.

The compound of formula (V) in any stoichiometric ratio be added.

In the preparation of the catalyst system according to the invention, a molar Ratio B: M between the compounds of formulas (I) and formula (IV) of 0.01 to 10,000 used. A molar ratio of 0.1 to 1000 is preferred a molar ratio of 1 to 100 is particularly preferably used. This can a compound of formula (V) in a molar ratio Al: M from 0.01 to 10,000 can also be added. A molar ratio of 0.1 to 1000 is preferred. a molar ratio of 1 to 100 is very particularly preferably used. The connections can be in contact with one another in any conceivable combination to be brought. One possible procedure is that a Organo transition metal compound of formula (IV) in an aliphatic or aromatic solvent is dissolved or suspended. After that, a connection of the formula (V) added in dissolved or in suspended form. The response time is between 1 minute and 24 hours, with a response time between 5 Minutes and 120 minutes is preferred. The reaction temperature is between -10 ° C and + 200 ° C, with a temperature between 0 ° C and 50 ° C is preferred. An organoboron compound of the formula (I) is then either in Substance or added in dissolved or in suspended form. The response time is between 1 minute and 24 hours, with a response time between 5 Minutes and 120 minutes is preferred. The reaction temperature is between -10 ° C and + 200 ° C, with a temperature between 0 ° C and 50 ° C preferred becomes. The individual components can also be in succession, in any Order in which the polymerization vessel is entered.  

The catalyst systems according to the invention can also be used in supported form become.

The carrier component of the catalyst system according to the invention can be a any organic or inorganic, inert solid, in particular a porous carriers such as talc, inorganic oxides and finely divided polymer powders (e.g. Polyolefins).

Suitable inorganic oxides can be found in groups 2, 3, 4, 5, 13, 14, 15 and 16 of the Periodic Table of the Elements. Examples of oxides preferred as carriers include silicon dioxide, aluminum oxide, and mixed oxides of the two elements and corresponding oxide mixtures. Other inorganic oxides that can be used alone or in combination with the last-mentioned preferred oxide carriers are, for. B. MgO, ZrO ₂ , TiO ₂ or B ₂ O ₃ , to name just a few.

The carrier materials used have a specific surface area in the range from 10 to 1000 m ² / g, a pore volume in the range from 0.1 to 5 ml / g and an average particle size from 1 to 500 μm. Carriers with a specific surface area in the range from 50 to 500 μm, a pore volume in the range between 0.5 and 3.5 ml / g and an average particle size in the range from 5 to 350 μm are preferred. Carriers with a specific surface area in the range from 200 to 400 m ² / g, a pore volume in the range between 0.8 to 3.0 ml / g and an average particle size of 10 to 200 μm are particularly preferred.

If the carrier material used is inherently low Moisture content or residual solvent content can cause dehydration or do not dry before use. If not, as with the use of silica gel as a carrier material is dehydration or Drying recommended. Thermal dehydration or drying of the Carrier material can be vacuumed and at the same time inert gas overlay (e.g. Nitrogen). The drying temperature is between 100 and 1000 ° C, preferably between 200 and 800 ° C. The pressure parameter is in not crucial in this case. The duration of the drying process can be between  1 and 24 hours. Shorter or longer drying times are possible provided that under the chosen conditions the equilibrium what can be done with the hydroxyl groups on the support surface usually takes between 4 and 8 hours.

Dehydration or drying of the carrier material is also chemical Possible by placing the adsorbed water and the hydroxyl groups on the Surface are reacted with suitable inerting agents. The hydroxyl groups can be reacted with the inerting reagent completely or partially converted into a form that does not lead to any lead to negative interaction with the catalytically active centers. suitable Inerting agents are, for example, silicon halides and silanes, such as Silicon tetrachloride, chlorotrimethylsilane, dimethylaminotrichlorosilane or organometallic compounds of aluminum, boron and magnesium such as for example trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, Triethylborane, dibutylmagnesium. Chemical dehydration or inertization of the carrier material takes place, for example, in that under air and Exclusion of moisture a suspension of the carrier material in a suitable Solvents with the inerting reagent in pure form or dissolved in one suitable solvent to react. Suitable solvents are e.g. B. aliphatic or aromatic hydrocarbons such as pentane, hexane, heptane, Toluene or xylene. Inerting takes place at temperatures between 25 ° C and 120 ° C, preferably between 50 ° C and 70 ° C. Higher and lower temperatures are possible. The duration of the reaction is between 30 minutes and 20 hours, preferably 1 to 5 hours. After the full chemical Dehydration becomes the carrier material by filtration under inert conditions isolated, one or more times with suitable inert solvents as before have been washed and then in an inert gas stream or on Vacuum dried.

Organic carrier materials such as fine-particle polyolefin powder (e.g. polyethylene, Polypropylene or polystyrene) can and should also be used before the use of adhering moisture, solvent residues or other  Contamination by appropriate cleaning and drying operations be freed.

The catalyst systems according to the invention can be brought into contact with the support in any conceivable combination. A conceivable variant is that an organometallic compound of the formula IV is placed in an aliphatic or aromatic solvent such as toluene, heptane, tetrahydrofuran or diethyl ether. Then one or more compounds of the formula (V) are added either in bulk or in dissolved form. The reaction time is between 1 minute and 24 hours, with a reaction time between 5 minutes and 120 minutes being preferred. The reaction temperature is between -10 ° C and + 200 ° C, with a temperature between 0 ° C and 50 ° C being preferred. Then one or more compounds of the formula (I) are added either in bulk or in dissolved form. Here too, the reaction time is between 1 minute and 24 hours, with a reaction time between 5 minutes and 120 minutes being preferred. The reaction temperature is between -10 ° C and + 200 ° C, with a temperature between 0 ° C and 50 ° C being preferred. All starting materials can be used in any stoichiometric ratio. A molar ratio Al: M ¹ between the compounds of the formula (V) and the formula (IV) of 0.1 to 10000 is preferred, and a molar ratio of 1 to 100 is very particularly preferably used. A molar ratio B: M1 between the compounds of the formula (I) and the formula (IV) of 0.1 to 1000 is preferred; a molar ratio of 1 to 100 is very particularly preferably used.

The preparation thus obtained is then dehydrated or rendered inert Mixed carrier material, the solvent removed and the resulting supported Metallocene catalyst system dried to ensure that the solvent completely or for the most part is removed from the pores of the carrier material. The supported catalyst is obtained as a free-flowing powder.

The present invention also relates to a method for producing a Polyolefins by polymerizing one or more olefins in the presence of the Catalyst system according to the invention, containing at least one  Transition metal component of formula (IV). The term polymerisation is used understood a homopolymerization as well as a copolymerization.

Olefins of the formula R _m -CH = CH-R _n are preferably polymerized, in which R _m and R _{n are} identical or different and denote a hydrogen atom or a carbon-containing radical having 1 to 20 C atoms, in particular 1 to 10 C atoms , and R _m and R _n together with the atoms connecting them can form one or more rings.

Examples of such olefins are 1-olefins with 2-40, preferably 2 to 10 Carbon atoms such as ethene, propene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1- pentene or 1-octene, styrene, dienes such as 1,3-butadiene, 1,4-hexadiene, vinyl norbornene Norbornadiene, ethylnorbornadiene and cyclic olefins such as norbornene, Tetracyclododecene or methylnorbornene. Are preferred in the Process according to the invention propene or ethene homopolymerized, or propene with ethene and / or with one or more 1-olefins having 4 to 20 carbon atoms, such as Witches, and / or one or more dienes with 4 to 20 carbon atoms, such as 1,4- Butadiene, norbornadiene, ethylidene norbones or ethyl norbornadiene, copolymerized. Examples of such copolymers are ethene / propene copolymers or Ethylene / propylene / 1,4-hexadiene terpolymers.

The polymerization is carried out at a temperature of -60 ° C to 300 ° C, preferably 50 ° C up to 200 ° C, very particularly preferably 50 ° C-80 ° C. The pressure is 0.5 to 2000 bar, preferably 5 to 64 bar.

The polymerization can be carried out in solution, in bulk, in suspension or in the gas phase, be carried out continuously or discontinuously, in one or more stages.

The catalyst system shown according to the invention can be the only one Catalyst component for the polymerization of olefins with 2 to 20 carbon atoms are used, or preferably in combination with at least one Alkyl compound of the elements from I. to III. Main group of the periodic table, such as B. an aluminum, magnesium or lithium alkyl or an aluminoxane be used. The alkyl compound is the monomer or  Suspending agent added and serves to purify the monomer from Substances that can impair catalyst activity. The amount of added alkyl compound depends on the quality of the monomers used. As a molecular weight regulator and / or to increase the activity, if necessary, Hydrogen added.

In the polymerization, an antistatic can also be combined with or separately metered into the polymerization system by the catalyst system used become.

The polymers shown with the catalyst system according to the invention show uniform grain morphology and no fine grain content. In the Polymerization with the catalyst system according to the invention occurs no deposits or caking.

With the catalyst system according to the invention, polymers such as polypropylene with extremely high stereo and regional specificity.

The isotactic polypropylene, which has been produced with the catalyst system according to the invention, is characterized by a proportion of 2-1-inserted propene units RI <0.5% with a triad tacticity TT <98.0% and a melting point <156 ° C., where M _W / M _{n of} the polypropylene according to the invention is between 2.5 and 3.5.

The copolymers which can be prepared using the catalyst system according to the invention are characterized by a significantly higher level compared to the prior art Molar mass. At the same time, such copolymers can be obtained by using the Catalyst system according to the invention with high productivity at technical relevant process parameters can be produced without deposit formation.

The polymers produced by the process according to the invention are in particular for the production of tear-resistant, hard and rigid moldings such as fibers, Filaments, injection molded parts, foils, plates or large hollow bodies (e.g. pipes) suitable.

The following examples serve to explain the invention in more detail

General information: The connections were made and handled with the exclusion of air and moisture under argon protection (Schlenk technology). All required solvents were boiled for several hours before use suitable desiccants and subsequent distillation under argon are absolute. to Characterization of the compounds were samples from each reaction blends removed and dried in an oil pump vacuum.

example 1 Synthesis of bis (pentafluorophenyloxy) methylalan (1)

5.2 ml of trimethylaluminum (2M in Exxol, 10.8 mmol) are placed in 40 ml of toluene and cooled to -40 ° C. 4.0 g (21.6 mmol) of pentafluorophenol in 40 ml of toluene are added dropwise to this solution over a period of 30 minutes. The mixture is stirred at -40 ° C. for 15 minutes and then the reaction solution is allowed to warm to room temperature. The mixture is stirred for one hour at room temperature. The result is a colorless solution (0.14M based on Al) of bis (pentafluorophenyloxy) methylalan.

¹⁹ F NMR (C ₆ D ₆ ): δ = -160.5 ppm (m, 4F, oC ₆ F ₅ ); -161.8 ppm (m, 2F, pC ₆ F ₅ ); -166.3 ppm (m, 4F, mC ₆ F ₅ ).

¹ H NMR (C ₆ D ₆ ): δ = -0.4 ppm (s, 3H, CH ₃ ).

Example 2 Synthesis of bis (pentafluorophenyloxy) ethylalan (2)

5.0 ml of triethyl aluminum (2.1M in vasol, 10.5 mmol) are placed in 40 ml of toluene and cooled to -40 ° C. 4.0 g (21.0 mmol) of pentafluorophenol in 40 ml of toluene are added dropwise to this solution over a period of 30 minutes. The mixture is stirred at -40 ° C. for 15 minutes and then the reaction solution is allowed to warm to room temperature. The mixture is stirred for one hour at room temperature. The result is a colorless solution (0.13M based on Al) of bis (pentafluorophenyloxy) ethylalan.

¹⁹ F NMR (C ₆ D ₆ ): δ = -160.9 ppm (m, 4F, oC ₆ F ₅ ); -162.1 ppm (m, 2F, pC ₆ F ₅ ); -167.3 ppm (m, 4F, mC ₆ F ₅ )

¹ H-NMR (C ₆ D ₆ ): δ = 0.5 ppm (t, 3H, CH ₃ ), 1.6 ppm (q, 2H, CH ₂ ).

Example 3 Synthesis of bis (pentafluoroaniline) methyalane (3)

5.0 ml of trimethylaluminum (2.1M in Exxol, 10.5 mmol) are placed in 40 ml of toluene and cooled to -40 ° C. 3.8 g (21.0 mmol) of pentafluoroaniline in 40 ml of toluene are added dropwise to this solution over a period of 30 minutes. The mixture is stirred at -40 ° C. for 15 minutes and then the reaction solution is allowed to warm to room temperature. The mixture is stirred at room temperature for two hours. The result is a yellowish solution (0.13M based on Al) of bis (pentafluoro aniline) methylalan.

¹⁹ F NMR (C ₆ D ₆ ): δ = -162.9 ppm (m, 4F, oC ₆ F ₅ ); -164.1 ppm (m, 2F, pC ₆ F ₅ ); -171.3 ppm (m, 4F, mC ₆ F ₅ )

¹ H NMR (C ₆ D ₆ ): δ = -0.4 ppm (t, 3H, CH ₃ ), 5.6 ppm (s, 1H, NH).

Example 4 Synthesis of bis (bis (pentafluorophenyl) methylene methyalane (4)

5.0 ml of trimethylaluminum (2.1M in Exxol, 10.5 mmol) are placed in 40 ml of toluene and cooled to -40 ° C. 7.6 g (21.0 mmol) of bis (pentafluorophenyl) carbinol in 40 ml of toluene are added dropwise to this solution over a period of 30 minutes. The mixture is stirred at -40 ° C. for 15 minutes and then the reaction solution is allowed to warm to room temperature on R 04482 00070 552 001000280000000200012000285910437100040 0002019917984 00004 04363. The mixture is stirred at room temperature for two hours. The result is a yellowish solution (0.13M based on Al) of bis (bis (pentafluorophenyl) methylene methyalane.

¹⁹ F NMR (C ₆ D ₆ ): δ = -140.6 ppm (m, 4F, o-CH (C ₆ F ₅ ) ₂ ); -151.7 ppm (m, 2F, p- CH (C ₆ F ₅ ) ₂ ); -159.5 ppm (m, 4F, m-CH (C ₆ F ₅ ) ₂ ).

¹ H NMR (C ₆ D ₆ ): δ = 6.2 ppm (s, 1H, CH).

Example 5 Synthesis of bis (3,5 bis (trifluoromethyl) aniline) methyalane (5)

5.0 ml of trimethylaluminum (2.1M in Exxol, 10.5 mmol) are placed in 40 ml of toluene and cooled to -40 ° C. 4.8 g (21.0 mmol) of 3.5 bis (trifluoromethyl) anilinin 40 ml of toluene are added dropwise to this solution over a period of 45 minutes. The mixture is stirred at -40 ° C. for 15 minutes and then the reaction solution is allowed to warm to room temperature. The mixture is stirred for four hours at room temperature. The slightly cloudy solution is filtered off via a G4 frit. The result is a yellowish, clear solution (0.13M based on Al) of bis (3,5 bis (trifluoromethyl) aniline) methyalane.

¹⁹ F NMR (C ₆ D ₆ ): δ = -61.5 ppm (s, 12F, CF ₃ ).

¹ H-NMR (C ₆ D ₆ ): δ = 5.5 ppm (s, 1H, NH), 6.3 ppm (s, 2H, Ar-H), 7.2 ppm (s, 1H, Ar-H).

Example 6 Synthesis of bis (nonanfluorodiphenyloxy) methyalane (6)

5.0 ml of trimethylaluminum (2.1M in Exxol, 10.5 mmol) are placed in 40 ml of toluene and cooled to -40 ° C. 7.0 g (21.0 mmol) of nonafluorodiphenyl-1-ol in 40 ml of toluene are added dropwise to this solution over a period of 40 minutes. The mixture is stirred at -40 ° C. for 30 minutes and then the reaction solution is allowed to warm to room temperature. The mixture is stirred for one hour at room temperature. The slightly cloudy solution is filtered off via a G4 frit. The result is a clear solution (0.13M based on Al) of bis (nonanfluorodiphenyloxy) methyalane.

¹⁹ F NMR (C ₆ D ₆ ): δ = -134.0 ppm (m, 2F, 2,2'-F); -137.2 ppm (m, 2F, 3, 3'-F);

-154.6 ppm (m, 2F, 4, 4'-F); 157.0 ppm (m, 1F, 6-F); 161.7 (m, 2F, 5, 5'-F).

¹ H NMR (C ₆ D ₆ ): δ = -0.3 ppm (s, 3H, CH ₃ ).

General description of catalyst manufacture and polymerization execution Manufacture of the catalyst system

1.25 ml of trimethylaluminum (2M in toluene) are added to a solution of 157 mg (250 μmol) of dimethylsilanediylbis (2-methyl-4-phenyl-indenyl) zirconium dichloride in 25 ml of toluene and the solution is stirred at room temperature for 30 minutes. Then 2 equivalents of the corresponding cocatalyst compound (500 μmol) are added dropwise. Then it is stirred for one hour at room temperature. 10.0 g of SiO ₂ (XPO2107, dried at 600 ° C. in a stream of argon) are added in portions to this solution. The mixture is stirred at RT for 30 minutes and the solvent is then removed in an oil pump vacuum. The result is a free-flowing powder. To infiltrate the polymerization system, 1 g of the supported catalyst system is resuspended in 30 ml of Exxol.

polymerization was

In parallel, a dry 16 dm ³ reactor is first flushed with nitrogen and then with propylene and filled with 10 dm ^{3 of} liquid propene. Then 0.5 cm ^{3 of} a 20% triisobutyl aluminum solution in Varsol diluted with 30 cm ³ Exxol were added to the reactor and the mixture was stirred at 30 ° C. for 15 minutes. The catalyst suspension was then added to the reactor. The reaction mixture was heated to the polymerization temperature of 60 ° C. (4 ° C./min) and the polymerization system was kept at 60 ° C. for 1 hour by cooling. The polymerization was stopped by venting the remaining porpylene. The polymer was dried in an oven.

polymerization

Claims (6)

1. compound of the general formula (I),
[(R ¹ ) -XM ¹ (R ³ ) -X- (R ² )] _k (I)
wherein
R ¹ , R ^{2 are the} same or different and are a hydrogen atom, a halogen atom, a boron-free C ₁ -C ₄₀ carbon-containing group such as C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ haloalkyl, C ₁ -C ₁₀ alkoxy , C ₆ -C ₂₀ aryl, C ₆ -C ₂₀ haloaryl, C ₆ -C ₂₀ aryloxy, C ₇ -C ₄₀ arylalkyl, C ₇ -C ₄₀ haloarylalky, C ₇ -C ₄₀ alkylaryl, C ₇ -C ₄₀ - haloalkylaryl or an Si (R ⁴ ) ₃ group,
R ^{4 is} a boron-free C ₁ -C ₄₀ carbon-containing group such as C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ haloalkyl, C ₁ -C ₁₀ alkoxy, C ₆ -C ₂₀ aryl, C ₆ -C ₂₀ Haloaryl, C ₆ -C ₂₀ aryloxy, C ₇ -C ₄₀ arylalkyl, C ₇ -C ₄₀ haloarylalkyl, C ₇ -C ₄₀ alkylaryl, C ₇ -C ₄₀ - haloalkylaryl,
R ³ can be identical or different to R ¹ and R ² , a hydrogen atom, a halogen atom, a C ₁ -C ₄₀ carbon-containing group such as C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ haloalkyl, C ₁ -C ₁₀ -Alkoxy, C ₆ -C ₂₀ aryl, C ₆ -C ₂₀ haloaryl, C ₆ -C ₂₀ aryloxy, C ₇ -C ₄₀ arylalkyl, C ₇ -C ₄₀ haloarylalkyl, C ₇ -C ₄₀ alkylaryl , C ₇ -C ₄₀ - haloalkylaryl or an OSi (R ⁴ ) ₃ group,
X identically or differently denotes an element from group IV, V or VIa of the periodic table of the elements or an NH group,
M ^{1 is} an element of group IIIa of the periodic table of the elements and
k is a natural number from 1 to 100 and 2. A process for the preparation of the compound of formula (I) according to claim 1, wherein one of the compounds of formula (II)
(R ⁵ ) ₃ Y (II)
wherein
R ^{5 is} a hydrogen atom or a boron-free C ₁ -C ₄₀ carbon-containing group such as C ₁ -C ₂₀ alkyl, C ₆ -C ₂₀ aryl, C ₇ -C ₄₀ arylalkyl, C ₇ -C ₄₀ alkylaryl or halogen atom can
Y boron or aluminum is reacted with a compound (III)
(R ⁶ ) X (R ¹ R ² ) (III)
wherein,
R ¹ and R ^{2 have} the meaning described under formula (I),
X is an oxygen, sulfur or an NH group,
R ^{6 is} hydrogen, C ₁ -C ₄₀ carbon-containing group or a p-toluenesulfonic acid radical. 3. Containing catalyst system

• A) at least one chemical compound of formula (I) according to claim 1
• B) at least one transition metal compound

4. A catalyst system according to claim 3 additionally containing a support. 5. Process for the preparation of a polyolefin in the presence of a Catalyst system according to claim 3 or 4. 6. Use of a catalyst system according to claim 3 or 4 for Olefin polymerization.