Metallocenes as catalysts in the preparation of cycloolefin copolymers

• US 5,990,254 A
• Filed: 12/26/1996
• Issued: 11/23/1999
• Est. Priority Date: 12/21/1993
• Status: Expired due to Fees

• Current Assignee: Targor Gmbh (BASF SE)
• Original Assignee: Targor Gmbh (BASF SE)
• Inventors: Psiorz, Christian, Weller, Thomas, Bachmann, Bernd, Erker, Gerhard, Aulbach, Michael, Osan, Frank, Kuber, Frank
• Primary Examiner(s): TESKIN, FRED M
• Application Number:
  US08/780,179
• Time in Patent Office: 1,062 Days
• Field of Search: 526/160, 526/170, 526/281, 526/943, 526/127, 526/161
• US Class Current: 526/160
• CPC Class Codes: C07F 17/00 Metallocenes
• CPC Class Codes: C08F 10/00 Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• CPC Class Codes: C08F 110/02 Ethene
• CPC Class Codes: C08F 110/06 Propene
• CPC Class Codes: C08F 210/06 Propene
• CPC Class Codes: C08F 210/16 Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
• CPC Class Codes: C08F 210/18 with non-conjugated dienes, e.g. EPT rubbers
• CPC Class Codes: C08F 2420/09 Cyclic bridge, i.e. Cp or analog where the bridging unit linking the two Cps or analogs is part of a cyclic group
• CPC Class Codes: C08F 2500/17 Viscosity
• CPC Class Codes: C08F 2500/25 Cycloolefine
• CPC Class Codes: C08F 4/61912 in combination with an organoaluminium compound
• CPC Class Codes: C08F 4/61927 two cyclopentadienyl rings being mutually bridged
• CPC Class Codes: C08F 4/65912 in combination with an organoaluminium compound
• CPC Class Codes: C08F 4/65927 two cyclopentadienyl rings being mutually bridged
• CPC Class Codes: Y10S 526/943 Polymerization with metallocene catalysts

Abstract

The present invention relates to a stereorigid metallocene compound containing, as ligands, at least two substituted or unsubstituted cyclopentadienyl groups which are bonded to one another via a monocyclic or polycyclic ring system, where at least one cyclopentadienyl group is fused to the monocyclic or polycyclic ring system, and to a process for the preparation of a cycloolefin copolymer. The cycloolefin copolymers obtained in this way have high tear strengths and are suitable for the production of extrusion parts and injection moldings.

Claims

1. A process for the preparation of a cycloolefin copolymer by polymerization of a) at least one polycyclic olefin, b) at least one acyclic 1-olefin and c), optionally, one or more monocyclic olefins, in the presence of a catalyst comprising at least one cocatalyst and at least one stereorigid metallocene compound, where the stereorigid metallocene compound contains, as ligands, at least two substituted or unsubstituted cyclopentadienyl groups which are bonded to one another via a monocyclic or polycyclic ring system, and in which at least one cyclopentadienyl group is fused to the monocyclic or polycyclic ring system.

2. The process as claimed in claim 1, in which the monocyclic or polycyclic ring system of the stereorigid metallocene compound has at least six ring atoms.

3. The process as claimed in claim 1, in which the cocatalyst is an aluminoxane.

4. The process as claimed in claim 1, in which the stereorigid metallocene compound is a compound of the formula I ##STR17## in which M¹ is a metal from group IIIb, IVb, Vb or VIb of the Periodic Table,

M² is carbon, silicon, or germanium,

R¹ and R² are identical or different and are a hydrogen atom, a C₁ -C₄₀ -hydrocarbon-containing group, an OH group, a halogen tom or NR¹⁴₂, in which R¹⁴ is a halogen atom, a C₁ -C₁₀ -aryl group, or R¹ and R² together with the atoms connecting them form a ring system,

R³, R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ are identical or different and are a hydrogen atom, a halogen atom, a C₁ -C₄₀ -hydrocarbon-containing group which optionally can be halogenated, a --SiR¹⁴₃, --NR¹⁴₂, --SiOR¹⁴₃, --SiSR¹⁴₃, or --PR¹⁴₂ radical, in which R¹⁴ is a halogen atom, a C₁ -C₁₀ -alkyl group or a C₆ -C₁₀ -aryl group, or two or more adjacent radicals R³, R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹, together with the atoms connecting them, form a ring system,

R¹⁰ is a hydrogen atom, a C₁ -C₄₀ -hydrocarbon-containing group, which may carry --NR¹⁴₃, --SiR¹⁴₃, --SR¹⁴₂, or --OSiR¹⁴₃ radicals, in which R¹⁴ is a halogen atom, a C₁ -C₁₀ -alkyl group or a C₆ -C₁₀ -aryl group, or R¹⁰ is connected to one or more of the radicals R³, R⁴, R⁵ and R⁶,

R¹¹ is ##STR18## where n is an integer from 1 to 20, l is an integer from 0 to 20, X is 0, ═

NR¹⁴, ═

CO, ═

PR¹⁴, ═

P(O)R¹⁴, ═

SO, ═

SO₂ or --S--, in which R¹⁴ is a halogen atom, a C₁ -C₁₀ -alkyl group or a C₆ -C₁₀ -aryl group,

R¹⁵ and R¹⁶ are identical or different and are a hydrogen atom, a halogen atom or a C₁ -C₄₀ -hydrocarbon-containing group, or two radicals R¹⁵, two radicals R¹⁶ or R¹⁵ and R¹⁶, in each case together with the atoms connecting them, form one or more rings, and M¹³ is silicon, germanium or tin, R¹² and R¹³ are identical or different and are a hydrogen atom, a C₁ -C₄₀ -hydrocarbon-containing group,

which may carry --NR¹⁴₃, --SR¹⁴₂, --SiR¹⁴₃, or --OSiR¹⁴₃ radicals, in which R¹⁴ is a halogen atom, a C₁ -C₁₀ -alkyl group or a C₆ -C₁₀ -aryl group, or may carry halogen,

R²³ is identical or different and is a hydrogen atom, a halogen atom or a C₁ -C₄₀ -hydrocarbon-containing group,

or one or more radicals R²³ are bonded to one or both radicals R¹⁵ and R¹⁶ and/or to one or more radicals R¹⁰, R¹¹, R¹² and R¹³, and

m is an integer from 0 to 24,

where, in the case where M² is C,, mis 0 and R¹¹ is CH₂, at least one of the radicals R⁴, R⁸, R¹⁰, R¹² and R¹³ is not alkyl and/or at least on of the radicals R³, R⁵, R⁶, R⁷ and R⁸ is not hydrogen.

5. The process as claimed in claim 4, in which M¹ is zirconium, R¹ and R² are identical and are a halogen atom, R³, R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ are identical or different and are hydrogen or a C₁ -C₄ -alkyl group or a C₆ -C₁₄ -aryl group, or R⁸ and R⁹ and R³ and R⁴ and/or R⁵ and R⁶, together with the atoms connecting them, form an aromatic hydrocarbon ring system, M² is a carbon atom, R¹⁰ is a C₁ -C₆ -alkyl group, R¹¹ is --CH₂ --CH₂ --, R¹² and R¹³ are identical or different and are a methyl or phenyl group, and m is 0.

6. The process as claimed in claim 4, wherein R¹ and R² are identical or different and are C₁ -C₁₀ alkyl group, a C₁ -C₁₀ alkoxy group, a C₆ -C₁₀ -aryl group, a C₆ -C₂₅ -aryloxy group, a C₂ -C₁₀ -alkenyl group, a C₇ -C₄₀ -arylalkyl group or a C₇ -C₄₀ -arylalkenyl group;

R³, R⁴, R⁵, R⁶, R⁷, R⁸, and R⁹ are identical or different and are a hydrogen atom, halogen atom, a C₁ -C₁₀ -alkyl group, which may be halogenated, a C₆ -C₂₀ -aryl group, a C₆ -C₂₀ -aryloxy group, a C₂ -C₁₂ -alkenyl group, a C₇ -C₄₀ -arylalkyl group, a C₇ -C₄₀ -alkylaryl group or a C₈ -C₄₀ -arylalkenyl group where two or more adjacent radicals are R³, R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ together with the atoms connecting them form a ring system containing 4 to 40 carbon atoms, R¹⁰ is a hydrogen atom, a C₁ -C₂₀ -alkyl group, a C₁ -C₁₀ -alkoxy group, a C₆ -C₂₀ -aryl group, a C₆ -C₂₀ -aryloxy group, a C₂ -C₁₂ -alkenyl group, a C₇ -C₄₀ -arylalkyl group, a C₇ -C₄₀ -alkylaryl group or a C₈ -C₄₀ -arylalkenyl group, each of which may carry --NR¹⁴₃, SiR¹⁴₃, --SR¹⁴₂ or --Osir¹⁴₃ radicals, in which R¹⁴ is a halogen atom, a C₁ -C₁₀ -alkyl group or a C₆ -C₁₀ -aryl group R¹⁵ and R⁶ are identical or different and are a hydrogen atom, a halogen atom or a C₁ -C₁₀ -alkyl group, a C₁ -C₁₀ -fluoroalkyl group, a C₁ -C₁₀ -alkoxy group, a C₆ -C₁₀ -aryl group, a C₆ -C₁₀ -fluoroaryl group, a C₆ -C₁₀ -aryloxy group, a C₂ -C₁₀ -alkenyl group, a C₇ -C₄₀ -arylalkyl group, a C₇ -C₄₀ -alkylaryl group, or a C₈ -C₄₀ -arylalkenyl group, R¹² and R¹³ are identical or different and a hydrogen atom C₁ -C₂₀ -alkyl group, a C₁ -C₁₀ -alkoxy group, a C₆ -C₂₀ -aryl group, a C₆ -C₂₀ -aryloxy group, a C₂ -C₁₂ -alkenyl group, a C₇ -C₄₀ -arylalkyl group, a C₇ -C₄₀ -alkylaryl group or a C₈ -C₄₀ -arylalkenyl group, each of which may carry --NR¹⁴₃, --SR¹⁴₂, --SiR¹⁴₃, or --OSiR¹⁴₃ radicals, in which R¹⁴ is a halogen atom, a C₁ -C₁₀ -alkyl group or a C₆ 14 C₁₀ -aryl group, or may carry halogen, R²⁰₃ is identical or different and is a hydrogen atom, a halogen atom, a C₁ -C₁₀ -alkyl group, a C₁ -C₁₀ -alkoxy group, a C₆ -C₁₀ -aryl group, a C₆ -C₂₅ -aryloxy group, a C₂ -C₁₀ -alkenyl group, a C₇ -C₄₀ -arylalkyl group or a C₇ -C₄₀ -arylalkenyl group.

7. The process as claimed in claim 6, wherein two or more adjacent radicals R³, R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ together with the atoms connecting them form a ring system containing 6 to 15 carbon atoms.

8. The process as claimed in claim 6, wherein M¹ zirconium or hafnium and R¹ are identical and R¹ -R³ alkyl or a halogen atom, R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹ are identical or different and are a hydrogen atom or C₁ -C₁₀ -alkyl group, or a C₆ -C₂₄ -aryl group, or two or more adjacent radicals together with the atoms connecting them form an aromatic or aliphatic hydrocarbon ring system, R¹⁰ is hydrogen, C₆ -C₂₄ -aryl group or a C₁ -C₁₀ -alkyl group, R¹¹ is ##STR19## wherein n is an integer form 1 to 8, R¹⁵ and R¹⁶ are identical or different and are hydrogen or a C₁ -C₁₀ -alkyl group, or two radicals R¹⁵, two radicals R¹⁶ or R¹⁵ and R¹⁶, together with the atoms connecting them, form a hydrocarbon ring system,

M² is carbon,

R¹² and R¹³ are identical or different and are a hydrogen atom, a C₁ -C₁₀ alkyl group, or a C₆ -C₁₀ aryl group and m is 0.

9. The process as claimed in claim 8, wherein R¹ and R² are chlorine, M¹ is zirconium, R¹⁰ is C₁ -C₄ -alkyl group, n is an integer from 2 to 4, R¹² and R¹³ are identical or different and are a hydrogen atom, a C₁ -C₄ -alkyl group or a C₆ -C₁₀ -aryl group.

10. The process as claimed in claim 9, wherein R³, R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ are identical or different and are halogen, a C₁ -C₄ -alkyl group, or C₆ -C₁₄ -aryl group, or R⁸ and R⁹ and R³ and R⁴ and/or R⁵ and R⁶ together with the atoms connecting them from aromatic hydrocarbon ring system may be substituted, R¹⁰ is a C₁ -C₆ -alkyl group, R¹¹ is --CH₂ --CH₂, R¹² and R¹³ are identical and different and are a methyl or phenyl group.

11. The process as claimed in claim 10, wherein R³, R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ are identical or different and are hydrogen, methyl, ethyl, isopropyl, butyl or isobutyl, phenyl or naphthyl or R⁸ and R⁹ and R³ and R⁴ and/or R⁵ and R⁶ together with the atoms connecting them form a 6-membered ring, R¹⁰ is methyl.

12. The process as claimed in claim 4, wherein at least one of the radicals R³ to R⁹ is not hydrogen.

13. The process as claimed in claim 11, wherein at least one of the radicals R³ to R⁹ is not hydrogen.

14. The process as claimed in claim 13, wherein at least one of the radicals R⁴, R⁵, or R⁸ is not hydrogen.

15. The process as claimed in claim 12, wherein at least one of the radicals R⁴, R⁵ or R⁸ is not hydrogen.

16. The process as claimed in claim 1, wherein the said metallocene compound is selected from the group consisting of

[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 -cyclopentadienyl)-4,7,7-triphenyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorotitanium,

[4-(η

⁵ -cyclopentadienyl)-4,7,7-triphenyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -cyclopentadienyl)-4,7-dimethyl-7-phenyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorotitanium,

[4-(η

⁵ -cyclopentadienyl)-4,7-dimethyl-7-phenyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -cyclopentadienyl)-4,7-dimethyl-7-naphthyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorotitanium,

[4-(η

⁵ -cyclopentadienyl)-4,7-dimethyl-7-naphthyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -cyclopentadienyl)-4,7-dimethyl-7-butyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorotitanium,

[4-(η

⁵ -cyclopentadienyl)-4,7-dimethyl-7-butyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-tert-butylcyclopentadienyl)-4,7,7-trimethyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorotitanium,

[4-(η

⁵ -3'"'"'-tert-butylcyclopentadienyl)-4,7,7-trimethyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-tert-butylcyclopentadienyl)-4,7,7-triphenyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorotitanium,

[4-(η

⁵ -3'"'"'-tert-butylcyclopentadienyl)-4,7,7-triphenyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-tert-butylcyclopentadienyl)-4,7-dimethyl-7-phenyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorotitanium,

[4-(η

⁵ -3'"'"'-tert-butylcyclopentadienyl)-4,7-dimethyl-7-phenyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-tert-butylcyclopentadienyl)-4,7-dimethyl-7-naphthyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorotitanium,

[4-(η

⁵ -3'"'"'-tert-butylcyclopentadienyl)-4,7-dimethyl-7-naphthyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-tert-butylcyclopentadienyl)-4,7-dimethyl-7-butyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorotitanium,

[4-(η

⁵ -3'"'"'-tert-butylcyclopentadienyl)-4,7-dimethyl-7-butyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -indenyl)-4,7,7-trimethyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorotitanium,

[4-(η

⁵ -indenyl)-4,7,7-trimethyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -indenyl)-4,7,7-triphenyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorotitanium,

[4-(η

⁵ -indenyl)-4,7,7-triphenyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -indenyl)-4,7-dimethyl-7-phenyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorotitanium,

[4-(η

⁵ -indenyl)-4,7-dimethyl-7-phenyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -indenyl)-4,7-dimethyl-7-naphthyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorotitanium,

[4-(η

⁵ -indenyl)-4,7-dimethyl-7-naphthyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -indenyl)-4,7-dimethyl-7-butyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorotitanium,

[4-(η

⁵ -indenyl)-4,7-dimethyl-7-butyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -cyclopentadienyl)-4,7,7-trimethyl (η

⁵ -4,5,6,7-tetrahydrofluorenyl)]dichlorotitanium,

[4-(η

⁵ -cyclopentadienyl)-4,7,7-trimethyl (η

⁵ -4,5,6,7-tetrahydrofluorenyl)]dichlorozirconium,

[4-(η

⁵ -cyclopentadienyl)-4,7,7-triphenyl (η

⁵ -4,5,6,7-tetrahydrofluorenyl)]dichlorotitanium,

[4-(η

⁵ -cyclopentadienyl)-4,7,7-triphenyl (η

⁵ -4,5,6,7-tetrahydrofluorenyl)]dichlorozirconium,

[4-(η

⁵ -cyclopentadienyl)-4,7-dimethyl-7-phenyl (η

⁵ -4,5,6,7-tetrahydrofluorenyl)]dichlorotitanium,

[4-(η

⁵ -cyclopentadienyl)-4,7-dimethyl-7-phenyl (η

⁵ -4,5,6,7-tetrahydrofluorenyl)]dichlorozirconium,

[4-(η

⁵ -cyclopentadienyl)-4,7-dimethyl-7-naphthyl (η

⁵ -4,5,6,7-tetrahydrofluorenyl)]dichlorotitanium,

[4-(η

⁵ -cyclopentadienyl)-4,7-dimethyl-7-naphthyl-(η

⁵ -4,5,6,7-tetrahydrofluorenyl)]dichlorozirconium,

[4-(η

⁵ -cyclopentadienyl)-4,7-dimethyl-7-butyl (η

⁵ -4,5,6,7-tetrahydrofluorenyl)]dichlorotitanium,

[4-(η

⁵ -cyclopentadienyl)-4,7-dimethyl-7-butyl (η

⁵ -4,5,6,7-tetrahydrofluorenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-methylcyclopentadienyl)-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)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-methylcyclopentadienyl)-4,7,7-triphenyl-(η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorotitanium,

[4-(η

⁵ -3'"'"'-methylcyclopentadienyl)-4,7,7-triphenyl-(η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-methylcyclopentadienyl)-4,7-dimethyl-7-phenyl-(η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorotitanium,

[4-(η

⁵ -3'"'"'-methylcyclopentadienyl)-4,7-dimethyl-7-phenyl-(η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-methylcyclopentadienyl)-4,7-dimethyl-7-naphthyl-(η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorotitanium,

[4-(η

⁵ -3'"'"'-methylcyclopentadienyl)-4,7-dimethyl-7-naphthyl-(η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-methylcyclopentadienyl)-4,7-dimethyl-7-butyl-(η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorotitanium,

[4-(η

⁵ -3'"'"'-methylcyclopentadienyl)-4,7-dimethyl-7-butyl-(η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -cyclopentadienyl)-4,7,7-trimethyl (η

⁵ -2-methyl-4,5,6,7-tetrahydroindenyl)]dichlorotitanium,

[4-(η

⁵ -cyclopentadienyl)-4,7,7-trimethyl (η

⁵ -2-methyl-4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -cyclopentadienyl)-4,7,7-triphenyl (η

⁵ -2-methyl-4,5,6,7-tetrahydroindenyl)]dichlorotitanium,

[4-(η

⁵ -cyclopentadienyl)-4,7,7-triphenyl (η

⁵ -2-methyl-4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -cyclopentadienyl)-4,7-dimethyl-7-phenyl (η

⁵ -2-methyl-4,5,6,7-tetrahydroindenyl)]dichlorotitanium,

[4-(η

⁵ -cyclopentadienyl)-4,7-dimethyl-7-phenyl (η

⁵ -2-methyl-4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -cyclopentadienyl)-4,7-dimethyl-7-naphthyl (η

⁵ -2-methyl-4,5,6,7-tetrahydroindenyl)]dichlorotitanium,

[4-(η

⁵ -cyclopentadienyl)-4,7-dimethyl-7-naphthyl (η

⁵ -2-methyl-4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -cyclopentadienyl)-4,7-dimethyl-7-butyl (η

⁵ -2-methyl-4,5,6,7-tetrahydroindenyl)]dichlorotitanium,

[4-(η

⁵ -cyclopentadienyl)-4,7-dimethyl-7-butyl (η

⁵ -2-methyl-4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-methylcyclopentadienyl)-4,7,7-trimethyl (η

⁵ -2-methyl-4,5,6,7-tetrahydroindenyl)]dichlorotitanium,

[4-(η

⁵ -3'"'"'-methylcyclopentadienyl)-4,7,7-trimethyl (η

⁵ -2-methyl-4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-methylcyclopentadienyl)-4,7,7-triphenyl (η

⁵ -2-methyl-4,5,6,7-tetrahydroindenyl)]dichlorotitanium,

[4-(η

⁵ -3'"'"'-methylcyclopentadienyl)-4,7,7-triphenyl (η

⁵ -2-methyl-4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-methylcyclopentadienyl)-4,7-dimethyl-7-phenyl (η

⁵ -2-methyl-4,5,6,7-tetrahydroindenyl)]dichlorotitanium,

[4-(η

⁵ -3'"'"'-methylcyclopentadienyl)-4,7-dimethyl-7-phenyl (η

⁵ -2-methyl-4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-methylcyclopentadienyl)-4,7-dimethyl-7-naphthyl (η

⁵ -2-methyl-4,5,6,7-tetrahydroindenyl)]dichlorotitanium,

[4-(η

⁵ -3'"'"'-methylcyclopentadienyl)-4,7-dimethyl-7-naphthyl (η

⁵ -2-methyl-4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-methylcyclopentadienyl)-4,7-dimethyl-7-butyl (η

⁵ -2-methyl-4,5,6,7-tetrahydroindenyl)]dichlorotitanium,

[4-(η

⁵ -3'"'"'-methylcyclopentadienyl)-4,7-dimethyl-7-butyl (η

⁵ -2-methyl-4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -fluorenyl)-4,7,7-trimethyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorotitanium,

[4-(η

⁵ -fluorenyl)-4,7,7-trimethyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -fluorenyl)-4,7,7-triphenyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorotitanium,

[4-(η

⁵ -fluorenyl)-4,7,7-triphenyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -fluorenyl)-4,7-dimethyl-7-phenyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorotitanium,

[4-(η

⁵ -fluorenyl)-4,7-dimethyl-7-phenyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -fluorenyl)-4,7-dimethyl-7-naphthyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorotitanium,

[4-(η

⁵ -fluorenyl)-4,7-dimethyl-7-naphthyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -fluorenyl)-4,7-dimethyl-7-butyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorotitanium,

[4-(η

⁵ -fluorenyl)-4,7-dimethyl-7-butyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -cyclopentadienyl)-4,7,7-trimethyl-4,5,6,7,10,11,12,13-octahydro-5,6-benzoindenyl) dichlorozirconium,

[5-(η

⁵ -cyclopentadienyl)-4,7,7-trimethyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorotitanium,

[5-(η

⁵ -cyclopentadienyl)-4,7,7-trimethyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[5-(η

⁵ -cyclopentadienyl)-4,7,7-triphenyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorotitanium,

[5-(η

⁵ -cyclopentadienyl)-4,7,7-triphenyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[5-(η

⁵ -cyclopentadienyl)-4,7-dimethyl-7-phenyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorotitanium,

[5-(η

⁵ -cyclopentadienyl)-4,7-dimethyl-7-phenyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[5-(η

⁵ -cyclopentadienyl)-4,7-dimethyl-7-naphthyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorotitanium,

[5-(η

⁵ -cyclopentadienyl)-4,7-dimethyl-7-naphthyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[5-(η

⁵ -cyclopentadienyl)-4,7-dimethyl-7-butyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorotitanium,

[5-(η

⁵ -cyclopentadienyl)-4,7-dimethyl-7-butyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[5-(η

⁵ -3'"'"'-tert-butylcyclopentadienyl)-4,7,7-trimethyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorotitanium,

[5-(η

⁵ -3'"'"'-tert-butylcyclopentadienyl)-4,7,7-trimethyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[5-(η

⁵ -3'"'"'-tert-butylcyclopentadienyl)-4,7,7-triphenyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorotitanium,

[5-(η

⁵ -3'"'"'-tert-butylcyclopentadienyl)-4,7,7-triphenyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[5-(η

⁵ -3'"'"'-tert-butylcyclopentadienyl)-4,7-dimethyl-7-phenyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorotitanium,

[5-(η

⁵ -3'"'"'-tert-butylcyclopentadienyl)-4,7-dimethyl-7-phenyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[5-(η

⁵ -3'"'"'-tert-butylcyclopentadienyl)-4,7-dimethyl-7-naphthyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorotitanium,

[5-(η

⁵ -3'"'"'-tert-butylcyclopentadienyl)-4,7-dimethyl-7-naphthyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[5-(η

⁵ -3'"'"'-tert-butylcyclopentadienyl)-4,7-dimethyl-7-butyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorotitanium,

[5-(η

⁵ -3'"'"'-tert-butylcyclopentadienyl)-4,7-dimethyl-7-butyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[5-(η

⁵ -indenyl)-4,7,7-trimethyl-(η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorotitanium,

[5-(η

⁵ -indenyl)-4,7,7-trimethyl(η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[5-(η

⁵ -indenyl)-4,7,7-triphenyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorotitanium,

[5-(η

⁵ -indenyl)-4,7,7-triphenyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[5-(η

⁵ -indenyl)-4,7-dimethyl-7-phenyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorotitanium,

[5-(η

⁵ -indenyl)-4,7-dimethyl-7-phenyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[5-(η

⁵ -indenyl)-4,7-dimethyl-7-naphthyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorotitanium,

[5-(η

⁵ -indenyl)-4,7-dimethyl-7-naphthyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[5-(η

⁵ -indenyl)-4,7-dimethyl-7-butyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorotitanium,

[5-(η

⁵ -indenyl)-4,7-dimethyl-7-butyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[5-(η

⁵ -cyclopentadienyl)-4,7,7-trimethyl (η

⁵ -4,5,6,7-tetrahydrofluorenyl)]dichlorotitanium,

[5-(η

⁵ -cyclopentadienyl)-4,7,7-trimethyl (η

⁵ -4,5,6,7-tetrahydrofluorenyl)]dichlorozirconium,

[5-(η

⁵ -cyclopentadienyl)-4,7,7-triphenyl (η

⁵ -4,5,6,7-tetrahydrofluorenyl)]dichlorotitanium,

[5-(η

⁵ -cyclopentadienyl)-4,7,7-triphenyl (η

⁵ -4,5,6,7-tetrahydrofluorenyl)]dichlorozirconium,

[5-(η

⁵ -cyclopentadienyl)-4,7-dimethyl-7-phenyl (η

⁵ -4,5,6,7-tetrahydrofluorenyl)]dichlorotitanium,

[5-(η

⁵ -cyclopentadienyl)-4,7-dimethyl-7-phenyl (η

⁵ -4,5,6,7-tetrahydrofluorenyl)]dichlorozirconium,

[5-(η

⁵ -cyclopentadienyl)-4,7-dimethyl-7-naphthyl (η

⁵ -4,5,6,7-tetrahydrofluorenyl)]dichlorotitanium,

[5-(η

⁵ -cyclopentadienyl)-4,7-dimethyl-7-naphthyl (η

⁵ -4,5,6,7-tetrahydrofluorenyl)]dichlorozirconium,

[5-(η

⁵ -cyclopentadienyl)-4,7-dimethyl-7-butyl (η

⁵ -4,5,6,7-tetrahydrofluorenyl)]dichlorotitanium,

[5-(η

⁵ -cyclopentadienyl)-4,7-dimethyl-7-butyl (η

⁵ -4,5,6,7-tetrahydrofluorenyl)]dichlorozirconium,

[5-(η

⁵ -fluorenyl)-4,7,7-trimethyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorotitanium,

[5-(η

⁵ -fluorenyl)-4,7,7-trimethyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[5-(η

⁵ -fluorenyl)-4,7,7-triphenyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorotitanium,

[5-(η

⁵ -fluorenyl)-4,7,7-triphenyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[5-(η

⁵ -fluorenyl)-4,7-dimethyl-7-phenyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorotitanium,

[5-(η

⁵ -fluorenyl)-4,7-dimethyl-7-phenyl (η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-isopropylcyclopentadienyl)-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -4'"'"'-isopropylcyclopentadienyl)-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-isopropylcyclopentadienyl)-2-isopropyl-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -4'"'"'-isopropylcyclopentadienyl)-2-isopropyl-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-isopropylcyclopentadienyl)-4,7-dimethyl-7-phenyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -4'"'"'-isopropyl-cyclopentadienyl)-4,7-dimethyl-7-phenyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-isopropylcyclopentadienyl)-2-isopropyl-4,7-dimethyl-7-phenyl-η

.sup.5 -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -4'"'"'-isopropylcyclopentadienyl)-2-isopropyl-4,7-dimethyl-7-phenyl-η

.sup.5 -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-trimethylsilylcyclopentadienyl)-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -4'"'"'-trimethylsilylcyclopentadienyl)-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-trimethylsilylcyclopentadienyl)-2-trimethylsilyl-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -4'"'"'-trimethylsilylcyclopentadienyl)-2-trimethylsilyl-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-(tert-butyldimethylsilyl)cyclopentadienyl)-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -4'"'"'-(tert-butyldimethylsilyl)cyclopentadienyl)-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-(tert-butyldimethylsilyl)cyclopentadienyl)-2-(tert-butyldimethylsilyl)-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -4'"'"'-(tert-butyldimethylsilyl)cyclopentadienyl)-2-(tert-butyldimethylsilyl)-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-trimethylsilylcyclopentadienyl)-4,7-dimethyl-7-phenyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -4'"'"'-trimethylsilylcyclopentadienyl)-4,7-dimethyl-7-phenyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-trimethylsilylcyclopentadienyl)-2-trimethylsilyl-4,7-dimethyl-7-phenyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -4'"'"'-trimethylsilylcyclopentadienyl)-2-trimethylsilyl-4,7-dimethyl-7-phenyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-phenylcyclopentadienyl)-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -4'"'"'-phenylcyclopentadienyl)-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-phenylcyclopentadienyl)-2-phenyl-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -4'"'"'-phenylcyclopentadienyl)-2-phenyl-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-phenylcyclopentadienyl)-4,7-dimethyl-7-phenyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -4'"'"'-phenylcyclopentadienyl)-4,7-dimethyl-7-phenyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-phenylcyclopentadienyl)-2-phenyl-4,7-dimethyl-7-phenyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -4'"'"'-phenylcyclopentadienyl)-2-phenyl-4,7-dimethyl-7-phenyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -4'"'"'-methylcyclopentadienyl)-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -4'"'"'-methylcyclopentadienyl)-2-methyl-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -4'"'"'-methylcyclopentadienyl)-2-methyl-4,7-dimethyl-7-phenyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -4'"'"'-tert-butylcyclopentadienyl)-2-tert-butyl-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-tert-butylcyclopentadienyl)-2-tert-butyl-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -4'"'"'-tert-butylcyclopentadienyl)-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-benzylcyclopentadienyl)-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -4'"'"'-benzylcyclopentadienyl)-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-benzylcyclopentadienyl)-2-benzyl-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -4'"'"'-benzylcyclopentadienyl)-2-benzyl-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -cyclopentadienyl)-4-butyl-7,7-dimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -cyclopentadienyl)-4-butyl-7-methyl-7-butyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -cyclopentadienyl)-4-methyl-7,7-dibutyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -cyclopentadienyl)-4-methyl-7-butyl-7-phenyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -cyclopentadienyl)-4-butyl-7-methyl-7-phenyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-isopropylcyclopentadienyl)-2-isopropyl-4-butyl-7,7-dimethyl-η

.sup.5 -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -4'"'"'-isopropylcyclopentadienyl)-2-isopropyl-4-butyl-7,7-dimethyl-η

.sup.5 -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-isopropylcyclopentadienyl)-2-isopropyl-4-butyl-7-butyl-7-methyl-η

.sup.5 -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -4'"'"'-isopropylcyclopentadienyl)-2-isopropyl-4-butyl-7-methyl-7-phenyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-isopropylcyclopentadienyl)-4-butyl-7-butyl-7-methyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -4'"'"'-isopropylcyclopentadienyl)-2-isopropyl-4-butyl-7-methyl-7-phenyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ cyclopentadienyl)-4,7-dimethyl-7-(2-propen-1-yl)-(η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-isopropylcyclopentadienyl)-4,7-dimethyl-7-(2-propen-1-yl)-(η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -cyclopentadienyl)-4,7-dimethyl-7-(3-(9-borabicyclo {3,3,1}nonyl-β

)propyl)-(η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-isopropylcyclopentadienyl)-4,7-dimethyl-7-(3-(9-borabicyclo {3,3,1}nonyl-β

)propyl)-(η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -4'"'"'-isopropylcyclopentadienyl)-4,7-dimethyl-7-(3-(9-borabicyclo {3,3,1}nonyl-β

)propyl)-(η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-tert-butylcyclopentadienyl)-4,7-dimethyl-7-(3-(9-borabicyclo {3,3,1}nonyl-β

)propyl)-(η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -4'"'"'-tert-butylcyclopentadienyl)-4,7-dimethyl-7-(3-(9-borabicyclo {3,3,1}nonyl-β

)propyl)-(η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-methylcyclopentadienyl)-4,7-dimethyl-7-(3-(9-borabicyclo {3,3,1}nonyl-β

)propyl)-(η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-isopropylcyclopentadienyl)-2-isopropyl-4,7-dimethyl-7-(3-(9-borabicyclo {3,3,1}nonyl-β

)propyl)-(η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -4'"'"'-isopropylcyclopentadienyl)-2-isopropyl-4,7-dimethyl-7-(3-(9-borabicyclo {3,3,1}nonyl-β

)propyl)-(η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-ethylcyclopentadienyl)-4,7,7-trimethyl-(η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -4'"'"'-ethylcyclopentadienyl)-4,7,7-trimethyl-(η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-ethylcyclopentadienyl)-2-ethyl-4,7,7,-trimethyl-(η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -4'"'"'-ethylcyclopentadienyl)-2-ethyl-4,7,7-trimethyl-(η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-isopropylcyclopentadienyl)-2-phenyl-4,7,7-trimethyl-(η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -4'"'"'-isopropylcyclopentadienyl)-2-phenyl-4,7,7-trimethyl-(η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-isopropylcyclopentadienyl)-2-methyl-4,7,7-trimethyl-(η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -4'"'"'-isopropylcyclopentadienyl)-2-methyl-4,7,7-trimethyl-(η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-isopropylcyclopentadienyl)-2-phenyl-4,7,7-trimethyl-(η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -4'"'"'-isopropylcyclopentadienyl)-2-phenyl-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -2-indenyl)-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -2-(4,5,6,7-tetrahydro)indenyl)-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -2-indenyl)-2-methyl-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -2-4,5,6,7-tetrahydro)indenyl)-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -2-indenyl)-2-phenyl-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -2-(4,5,6,7-tetrahydro)indenyl)-2-butyl-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -2-indenyl)-2-trimethylsilyl-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -2-(4,5,6,7-tetrahydro)indenyl)-2-trimethylsilyl-4,7,7-trimethyl-η

.sup.5 -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -2-indenyl)-2-isopropyl-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -2-(4,5,6,7-tetrahydro)indenyl)-2-methyl-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -2-indenyl)-2-butyl-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -2-(4,5,6,7-tetrahydro)indenyl)-2-phenyl-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-isopropylcyclopentadienyl)-2-methyl-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -4'"'"'-isopropylcyclopentadienyl)-2-methyl-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-isopropylcyclopentadienyl)-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydrofluorenyl)]dichlorozirconium,

[4-(η

⁵ -4'"'"'-isopropylcyclopentadienyl)-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydrofluorenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-isopropylcyclopentadienyl)-2-isopropyl-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydrofluorenyl)]dichlorozirconium,

[4-(η

⁵ -4'"'"'-isopropylcyclopentadienyl)-2-isopropyl-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydrofluorenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-butylcyclopentadienyl)-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -4'"'"'-butylcyclopentadienyl)-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-butylcyclopentadienyl)-2-isopropyl-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -4'"'"'-butylcyclopentadienyl)-2-isopropyl-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-butylcyclopentadienyl)-2-butyl-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -4'"'"'-butylcyclopentadienyl)-2-butyl-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"',4'"'"'-dimethylcyclopentadienyl)-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"',4'"'"'-diisopropylcyclopentadienyl)-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"',4'"'"'-diphenylcyclopentadienyl)-2-isopropyl-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"',4'"'"'-diethylcyclopentadienyl)-2-isopropyl-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"',4'"'"'-dibutylcyclopentadienyl)-2-isopropyl-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-methyl-4'"'"'-phenylcyclopentadienyl)-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-ethyl-4'"'"'-phenylcyclopentadienyl)-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-isopropyl-4'"'"'-phenylcyclopentadienyl)-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-methyl-4'"'"'-isopropylcyclopentadienyl)-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium,

[4-(η

⁵ -3'"'"'-methyl-4'"'"'-naphthylcyclopentadienyl)-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium, and

[4-(η

⁵ -3'"'"'-methyl-4'"'"'-butylcyclopentadienyl)-4,7,7-trimethyl-η

⁵ -4,5,6,7-tetrahydroindenyl)]dichlorozirconium.

17. The process as claimed in claim 1, wherein the compound is selected from the group consisting of

[η

⁵ -9-(η

⁵ -cyclopentadienyl)tricyclo[6.1.1.0²,6 ]deca-2,5-dienyl]dichlorotitanium,

[η

⁵ -9-(η

⁵ -cyclopentadienyl)tricyclo[6.1.1.0²,6 ]deca-2,5-dienyl]dichlorozirconium,

[η

⁵ -7-methyl-9-(η

⁵ -cyclopentadienyl)tricyclo[6.1.1.0²,6 ]deca-2,5-dienyl]dichlorotitanium,

[η

⁵ -7-methyl-9-(η

⁵ -cyclopentadienyl)tricyclo[6.1.1.0²,6 ]deca-2,5-dienyl]dichlorozirconium,

[η

⁵ -9-methyl-9-(η

⁵ -cyclopentadienyl)tricyclo[6.1.1.0²,6 ]deca-2,5-dienyl]dichlorotitanium,

[η

⁵ -9-methyl-9-(η

⁵ -cyclopentadienyl)tricyclo[6.1.1.0²,6 ]deca-2,5-dienyl]dichlorozirconium,

[η

⁵ -10-(η

⁵ -cyclopentadienyl)tricyclo[5.2.1.0²,6 ]deca-2,5-dienyl]dichlorotitanium,

[η

⁵ -10-(η

⁵ -cyclopentadienyl)tricyclo[5.2.1.0²,6 ]deca-2,5-dienyl]dichlorozirconium,

[η

⁵ -10-methyl-10-(η

⁵ -cyclopentadienyl)tricyclo[5.2.1.0²,6 ]deca-2,5-dienyl]dichlorotitanium,

[η

⁵ -10-methyl-10-(η

⁵ -cyclopentadienyl)tricyclo[5.2.1.0²,6 ]deca-2,5-dienyl]dichlorozirconium,

[η

⁵ -9-(η

⁵ -cyclopentadienyl)tricyclo[5.2.2.0²,6 ]undeca-2,5-dienyl]dichlorotitanium,

[η

⁵ -9-(η

⁵ -cyclopentadienyl)tricyclo[5.2.2.0²,6 ]undeca-2,5-dienyl]dichlorozirconium,

[η

.sup. -9-methyl-9-(η

⁵ -cyclopentadienyl)tricyclo[5.2.2.0²,6 ]-undeca-2,5-dienyl]dichlorotitanium,

[η

⁵ -9-methyl-9-(η

⁵ -cyclopentadienyl)tricyclo[5.2.2.0²,6 ]-undeca-2,5-dienyl]dichlorozirconium,

[η

⁵ -10-(η

⁵ -3'"'"'-methylcyclopentadienyl)tricyclo[5.2.1.0²,6 ]-deca-2,5-dienyl]dichlorotitanium,

[η

⁵ -10-(η

⁵ -3'"'"'-methylcyclopentadienyl)tricyclo[5.2.1.0²,6 ]-deca-2,5-dienyl]dichlorozirconium,

[η

⁵ -10-methyl-10-(η

⁵ -3'"'"'-methylcyclopentadienyl)tricyclo[5.2.1.0²,6 ]deca-2,5-dienyl]dichlorotitanium,

[η

⁵ -10-methyl-10-(η

⁵ -3'"'"'-methylcyclopentadienyl)tricyclo[5.2.1.0²,6 ]deca-2,5-dienyl]dichlorozirconium,

[η

⁵ -4-methyl-10-(η

⁵ -3'"'"'-methylcyclopentadienyl)tricyclo[5.2.1.0²,6 ]deca-2,5-dienyl]dichlorotitanium,

[η

⁵ -4-methyl-10-(η

⁵ -3'"'"'-methylcyclopentadienyl)tricyclo[5.2.1.0²,6 ]deca-2,5-dienyl]dichlorozirconium,

[η

⁵ -4,10-dimethyl-10-(η

⁵ -3'"'"'-methylcyclopentadienyl)tricyclo[5.2.1.0²,6 ]deca-2,5-dienyl]dichlorotitanium,

[η

⁵ -4,10-dimethyl-10-(η

⁵ -3'"'"'-methylcyclopentadienyl)tricyclo[5.2.1.0²,6 ]deca-2,5-dienyl]dichlorozirconium,

[η

⁵ -5-methyl-10-(η

⁵ -3'"'"'-methylcyclopentadienyl)tricyclo[5.2.1.0²,6 ]deca-2,5-dienyl]dichlorotitanium,

[η

⁵ -5-methyl-10-(η

⁵ -3'"'"'-methylcyclopentadienyl)tricyclo[5.2.1.0²,6 ]deca-2,5-dienyl]dichlorozirconium,

[η

⁵ -5,10-dimethyl-10-(η

⁵ -3'"'"'-methylcyclopentadienyl)tricyclo[5.2.1.0²,6 ]deca-2,5-dienyl]dichlorotitanium, and

[η

⁵ -5,10-dimethyl-10-(η

⁵ -3'"'"'-methylcyclopentadienyl)tricyclo[5.2.1.0²,6 ]deca-2,5-dienyl]dichlorozirconium.

18. The process as claimed in claim 1, wherein said stereorigid metallocene compound contain as ligands, at least two substituted or unsubstituted cyclopentadienyl groups bonded to one another via a monocyclic ring system, in which at least one cyclopentadienyl group is fused to the monocyclic ring system and one cyclopentadienyl group is a substituent on the monocyclic ring system.

19. The process as claimed in claim 1, wherein said stereorigid metallocene compound contains as ligands, at least two substituted or unsubstituted cyclopentadienyl groups bonded to one another via a polycyclic ring system, in which at least one cyclopentadienyl group is fused to the polycyclic ring system.