Metallocene compounds, processes for the preparation thereof, catalyst components for olefin polymerization, and processes for the production of olefin polymers

Abstract

A metallocene compound is provided wherein to a transition metal compound is bonded a multidentate compound wherein a substituted cycloalkadienyl ring CA1 having therein a heteroaromatic group Ra containing an oxygen, sulfur or nitrogen atom on a cycloalkadienyl ring, preferably the five-membered ring thereof, and an unsubstituted or substituted cycloalkadienyl group CA2 or —(R1)N—, —O—, —S— or —(R1)P—, preferably CA2, more preferably a substituted cycloalkadienyl group identical with CA1 are bonded through a divalent linking group. The metallocene compound is suitable as a principal ingredient of a catalyst for the polymerization of olefins, particularly achieving a very high effect in making the molecular weight of a polypropylene higher.

Description

TECHNICAL FIELD

This invention relates to new metallocene compounds useful as a catalyst component for olefin polymerization. More particularly, the invention relates to metallocene compounds wherein a multidentate compound containing a cycloalkadienyl ring substituted by a heteroaromatic group is coordinated to a Group VIB transition metal atom of the Periodic Table, and also to the processes for the preparation thereof.

Further, the invention relates to catalysts for olefin polymerization containing said metallocene compounds and processes for the production of olefin polymers using them.

BACKGROUND ART

As a catalyst substituted for Ziegler-Natta catalysts which have been used in the polymerization of olefins, a part of the metallocene compounds is being used which consist of a complex compound wherein a multidentate compound containing a i-electron donor such as unsubstituted or substituted cycloalkadienyl groups is coordinated to a transition metal atom, the unsubstituted or substituted cycloalkadienyl groups including e.g., unsubstituted or substituted cyclopentadienyl groups, unsubstituted or substituted indenyl groups, unsubstituted or substituted tetrahydroindenyl groups, and unsubstituted or substituted fluorenyl groups.

In recent years, various metallocene compounds have been proposed having higher olefin polymerization activity per mole of a transition metal atom. It is known that the polymers of α-olefin having 3 or more carbon atoms, in particular, propylene polymers, prepared by using a chiral metallocene compound have high stereoregularity, the chiral metallocene compound being the compound wherein a multidentate compound having two substituted cycloalkadienyl groups bonded with a divalent linking group is coordinated to a transition metal atom (J. Am. Chem. Soc. 1998, 120, 11316-11322).

Further, the development of metallocene compounds with high olefin polymerization activity has continued. Various metallocene compounds have been proposed wherein a heteroatom is introduced into the substituent or cycloalkadiene ring in the substituted cycloalkadienyl group.

For instance, Japanese Patent Kokai 7-258282 discloses metallocene compounds wherein the 2-position of the indenyl group is substituted by a saturated group containing a heteroatom such as nitrogen, phosphorus, arsenic, antimony, bismuth or the like, specifically those wherein 2-pyrrolidino-1-indene is linked through a divalent linking group and coordinated to a transition metal atom.

Japanese Patent Kokai 8-183814 discloses chiral metallocene compounds wherein the 4-position of the indenyl group is substituted by unsubstituted or substituted 1-pyrrolyl group, 1-indolyl group or the like, specifically those wherein 4-(1-indolyl)-2-methylindene is linked through a divalent linking group and coordinated to a transition metal atom.

J. Am. Chem. Soc. 1998, 120, 10786-10787 discloses metallocene compounds wherein a heteroatom-containing cycloalkadiene having a thiophene ring or a pyrrol ring condensed to a cyclopentadiene ring is linked through a divalent linking group and coordinated to a transition metal atom.

DISCLOSURE OF THE INVENTION

As mentioned above, there are various proposals for introducing a heteroatom into a π-electron donor. Except for the compounds disclosed in Japanese Patent Kokai 8-183814, however, the metallocene compounds are not known wherein the substituted cycloalkadienyl group-containing compounds having a heteroaromatic group containing an oxygen atom, a sulfur atom or a nitrogen atom on a cycloalkadiene ring, particularly on the 5-membered ring thereof are coordinated to a transition metal atom.

The present invention provides a metallocene compound represented by the following formula (1)

wherein CA 1 represents a cycloalkadienyl group selected from the group consisting of a cyclopentadienyl group, an indenyl group, a tetrahydroindenyl group, a benzoindenyl group, a fluorenyl group and an azulenyl group;

each R 1 represents independently a halogen atom, a hydrocarbon group of 1-20 carbons, a halogenated hydrocarbon group wherein a part or all of the hydrogen atoms in the hydrocarbon group are substituted by a halogen atom, a silyl group substituted by said hydrocarbon group or said halogenated hydrocarbon group, an amino group substituted by said hydrocarbon group or a monocyclic or polycyclic amino group;

each Ra represents independently a monocyclic or polycyclic heteroaromatic group containing a heteroatom selected from the group consisting of an oxygen atom, a sulfur atom and a nitrogen atom in a 5- or 6-membered ring, the heteroaromatic group being optionally substituted by R 1 as defined above;

p is an integer of 1-8;

m is 0 or an integer of 1-8;

Z represents a linking group selected from the group consisting of (CA 7 )(R 1 ) m (Ra) p , (CA 2 )(Ra) q (R 1 ) n , —O—, —S—, —NR 1 — and —PR 1 — wherein CA 2 represents an unsubstituted or substituted cycloalkadienyl group; Ra and R 1 have the same meanings as defined above, Ra may be identical with or different from said Ra on CA 1 and R 1 may be identical with or different from said R 1 on CA 1 ; and q and n are each independently 0 or an integer of 1-8;

Y represents a divalent linking group selected from the group consisting of —C(R 2 ) 2 —, —C 2 (R 2 ) 4 —, —C 6 (R 2 ) 10 —, —C 6 (R 2 ) 4 —, —Si(R 2 ) 2 —, —Ge(R 2 ) 2 — and —Sn(R 2 ) 2 — wherein each R 2 represents independently a hydrogen atom, a halogen atom, a hydrocarbon group of 1-20 carbons, a halogenated hydrocarbon group wherein a part or all of the hydrogen atoms in the hydrocarbon group are substituted by a halogen atom or a silyl group substituted by said hydrocarbon group or said halogenated hydrocarbon group;

M represents a transition metal atom selected from the group consisting of Ti, Zr and Hf; and

each X 1 represents independently a halogen atom, a hydrocarbon group of 1-20 carbons, a halogenated hydrocarbon group wherein a part or all of the hydrogen atoms in the hydrocarbon group are substituted by a halogen atom or a silyl group substituted by said hydrocarbon group or said halogenated hydrocarbon group.

The present invention also provides a process for the preparation of said metallocene compound.

Further, the invention provides a catalyst for olefin polymerization comprising said metallocene compound and an aluminoxane. The invention further provides a process for the production of an olefin polymer wherein an olefin is polymerized in the presence of said olefin polymerization catalyst and in the presence or absence of an organic aluminum compound.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is 1 H-NMR chart determined in deuteriochloroform for compound No. 95 synthesized in Example 3, rac-dimethylsilylenebis[2-(2-furyl)-4,5-dimethylcyclopentadienyl]zirconium dichloride.

FIG. 2 is an ORTEP diagram obtained from a single crystal, X-ray structural analysis of compound No. 94 synthesized in Example 2, rac-dimethylsilylenebis[2-(2-furyl)-3,5-dimethylcyclopentadienyl]zirconium dichloride.

FIG. 3 is a scheme for synthesis illustrating an embodiment of the processes for the preparation of the metallocene compounds according to the present invention.

DETAILED DESCRIPTION

The metallocene compounds of the present invention represented by the formula (1) are largely classified into the compounds having a fundamental structure wherein Z is (Ra) p (R 1 ) m (CA 1 ) or (Ra) q (R 1 ) n (CA 2 ) and the compounds having a fundamental structure wherein Z is selected from —O—, —S—, —NR 1 — and —PR 1 —.

The cycloalkadienyl group CA includes a cyclopentadienyl group, an indenyl group, a tetrahydroindenyl group, a benzoindenyl group, a fluorenyl group or an azulenyl group.

In the present invention, one or more hydrogens in the cycloalkadienyl group CA 1 are substituted by the heteroaromatic group Ra which may be substituted by the substituent R 1 as defined above.

The heteroaromatic group Ra which substitutes a hydrogen atom on CA 1 and CA 2 is the groups containing as a heteroatom an oxygen atom, a sulfur atom or a nitrogen atom in the 5- or 6-membered ring. Preferable heteroaromatic groups include furyl, thienyl, pyridyl, benzofuryl, benzothienyl, quinolyl, pyrrolyl or indolyl having a bond at other positions than the 1-position, and those groups substituted by the substituent R 1 as recited later. In case of the heteroaromatic group being substituted by the substituent R 1 , for example, furyl is preferably substituted at the 4- or 5-position, most preferably at the 5-position. Where CA 1 and CA 2 are respectively substituted by one or more Ra, each Ra may be identical or different.

Preferably, the heteroaromatic group Ra substitutes a hydrogen atom on the 5-membered ring in the cycloalkadienyl group CA 1 . More preferably, the group Ra substitutes a hydrogen atom at the 2- and/or 3-position of the cyclopentadienyl group. Preferable substituted cycloalkadienyl group CA 1 includes a substituted cyclopentadienyl group, a substituted indenyl group, a substituted tetrahydroindenyl and a substituted benzoindenyl group, more preferably a substituted cyclopentadienyl group and a substituted indenyl group.

p indicates the number of substitution by the heteroaromatic group Ra on the cycloalkadienyl group CA 1 , and is an integer of 1 to 8, preferably 1 to 4, more preferably 1 or 2.

CA 2 in (Ra) q (R 1 ) n (CA 2 ) selected for the group Z is an unsubstituted or substituted cycloalkadienyl group. The cycloalkadienyl group CA 2 includes a cyclopentadienyl group, an indenyl group, a tetrahydroindenyl group, a benzoindenyl group and a fluorenyl group. The substituted cycloalkadienyl groups CA 2 are those wherein one or more hydrogen atoms on the cycloalkadienyl group are substituted by either or both of the heteroaromatic group Ra and the substituent R 1 .

For the case where CA 2 is the cycloalkadienyl group substituted by the heteroaromatic group Ra, it is preferable that the heteroaromatic group Ra substitutes a hydrogen atom on the 5-membered ring in the cycloalkadienyl group.

q indicates the number of substitution by the heteroaromatic group Ra on CA 2 , and is 0 or an integer of 1 to 8, preferably 1 to 4, more preferably 1 or 2.

The substituents R 1 on CA 1 and CA 2 include a halogen atom, e.g., fluorine, chlorine, bromine or iodine; a hydrocarbon group of 1-20 carbons, e.g., an alkyl group of 1-20 carbons, an aryl group of 6-20 carbons, an aralkyl group of 7-20 carbons, an alkoxy group of 1-20 carbons, an aryloxy group of 6-20 carbons or an aralkyloxy group of 7-20 carbons; a halogenated hydrocarbon group wherein a part or all of the hydrogen atoms in said hydrocarbon group are substituted by said halogen atom; a silyl group tri-substituted by said hydrocarbon group and/or said halogenated hydrocarbon group; an amino group di-substituted by said hydrocarbon group; and a monocyclic or polycyclic amino group. Where CA 1 and CA 2 are respectively substituted by one or more R 1 , each R 1 may be identical or different.

m and n indicate the number of substitution by R 1 on CA 1 and CA 2 , and are respectively 0 or an integer of 1 to 8, preferably 1 to 4, more preferably 1 or 2.

The alkyl group of 1-20 carbons includes, for example, a straight- or branched-chain alkyl group, e.g., methyl, ethyl, propyl, i-propyl, n-butyl, i-butyl, tert-butyl, sec-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, dodecyl or octadecyl; and a cyclic alkyl group which may be substituted by said chain alkyl group, e.g., cyclopropyl, cycloheptyl or cyclohexyl.

The aryl group of 6-20 carbons may be unsubstituted or substituted by said alkyl group, which includes, for example, phenyl, naphthyl, anthryl, tolyl, xylyl and trimethylphenyl. The aralkyl group of 7-20 carbons may be unsubstituted or substituted by said alkyl group, which includes, for example, benzyl, naphthylmethyl, anthrylmethyl, (methylphenyl)methyl, (dimethylphenyl)methyl, (trimethylphenyl)methyl, (ethylphenyl)methyl, (propylphenyl)methyl and (butylphenyl)methyl.

The alkoxy group of 1-20 carbons includes chain and cyclic alkoxy groups wherein the alkyl moiety is said alkyl group, e.g., methoxy, ethoxy, propoxy, isopropoxy, butoxy, t-butoxy, hexyloxy or cyclohexyloxy. The aryloxy group of 6-20 carbons includes substituted or unsubstituted aryloxy groups wherein the aryl moiety is said aryl group, e.g., phenoxy, naphthyloxy or anthryloxy. The aralkyloxy group of 7-20 carbons includes aralkyloxy groups wherein the aralkyl moiety is said aralkyl group, e.g., benzyloxy.

The halogenated hydrocarbon groups are those wherein a part or all of the hydrogen atoms in said hydrocarbon groups are substituted by said halogen atom, which include halogenated alkyl groups, halogenated aryl groups, halogenated aralkyl groups, halogenated alkoxy groups, halogenated aryloxy groups and halogenated aralkyloxy groups, e.g., monochloromethyl, dichloromethyl, trichloromethyl, perfluoroethyl, monochlorophenyl, difluorophenyl or monochlorobenzyl.

The substituted silyl groups are those substituted by said hydrocarbon group and/or said halogenated hydrocarbon group, e.g., trimethylsilyl, triethylsilyl, triphenylsilyl, trimethoxysilyl, tribenzylsilyl, triethoxysilyl, dimethylphenoxysilyl, dimethylvinylsilyl and allyldimethylsilyl.

The substituted amino groups are those substituted by said hydrocarbon group, e.g., dimethylamino, diethylamino and methylethylamino. The monocyclic or polycyclic amino groups may be saturated or unsaturated, which include, e.g., 1-pyrrolidyl, 1-pyrrolyl and 1-indolyl.

The divalent linking group Y includes —C(R 2 ) 2 —, e.g., methylene; —C 2 (R 2 ) 4 —, e.g., ethylene; —C 6 (R 2 ) 10 —, e.g., cyclohexylene; —C 6 (R 2 ) 4 —, e.g., phenylene; —Si(R 2 ) 2 —, e.g., silylene; —Ge(R 2 ) 2 —, e.g., germanylene; and —Sn(R 2 ) 2 —, e.g., stanylene wherein R 2 is as defined above.

Preferred linking group Y is —C(R 2 ) 2 —, e.g., methylene, dichloromethylene, dimethylmethylene and diphenylmethylene; —C 2 (R 2 ) 4 —, e.g., ethylene, tetrachloroethylene, tetramethylethylene, tetraethylethylene and dimethyldiphenylethylene; —Si(R 2 ) 2 —, e.g., dichlorosilylene, dimethylsilylene and diethylsilylene; and —Ge(R 2 ) 2 —, e.g., dichlorogermanylene and dimethylgermanylene.

The transition metal atom M is selected from the group consisting of Ti, Zr and Hf.

The substituent X 1 for M is a hydrogen atom, a halogen atom, a similar hydrocarbon or halogenated hydrocarbon group as defined above for the substituent R 1 , preferably a halogen atom, more preferably chlorine.

The metallocene compound of formula (1) wherein Z is (CA 2 )(R 1 ) n (Ra) q can be represented by the following formula (2)

wherein each symbol has the meaning as defined above.

CA 1 and CA 2 in the formula may be identical or different. In addition to the identity of CA 1 with CA 2 , the compound of the following formula (2A) wherein Z is (Ra) p (R 1 ) m (CA 1 ) in formula (1) shows high olefin polymerization activity excellent as the below-mentioned catalyst for olefin polymerization.

wherein each symbol has the meaning as defined above. This compound (2A) includes a racemic form consisting of a stereostructurally unsymmetrical compound with respect to the plane containing M and its enantiomer, a mesa form consisting of a stereostructurally symmetrical compound with respect to the plane containing M, and the mixture thereof.

The metallocene compounds wherein concrete combination of CA 1 and CA 2 is specified are represented by the following formulas (2a) to (2g).

Further, concrete examples of metallocene compounds represented by formula (2a) are shown in the attached Tables 2-9 and 23, concrete examples of metallocene compounds represented by formula (2d) are shown in the attached Tables 10-13 and 22, concrete examples of metallocene compounds represented by formula (2e) are shown in the attached Tables 14-17, concrete examples of metallocene compounds represented by formula (2g) are shown in the attached Tables 18, 19 and 24, and concrete examples of metallocene compounds represented by formula (2h) are shown in the attached Table 25, by way of indicating concrete groups corresponding to each symbol in each formula and without distinction of the racemic and meso forms.

For instance, the compound denoted by Number 1 in Table 2 represents ethylenebis[2-(2-furyl)-cyclopentadienyl][2′-(2-furyl)-cyclopentadienyl]zirconium dichloride, ethylenebis[2-(2-furyl)-cyclopentadienyl][5′-(2-furyl)-cyclopentadienyl]zirconium dichloride and the mixture thereof. For the compounds wherein the substituent R 1 is present on both CA 1 and CA 2 , they represent the compounds having the relationship of the racemic form and the meso form from a substitution position of each substituent R 1 on CA 1 and CA 2 , and the mixture thereof.

The abbreviations used in Tables 2-25 are as follows:

Fu: furyl,        MeFu: methyl furyl,
Thie: thienyl,    Py: pyridyl,
BzFu: benzofuryl, 1-MePyr: 1-methylpyrrolyl,
Me: methyl,       Et: ethyl,
i-Pr: isopropyl,  t-Bu: tert-butyl,
Ph: phenyl,       Np: naphthyl,
Tol: toluyl       Bzl: benzyl,
OMe: methoxy,     OPh: phenoxy,
OBzl: benzyloxy,  TMS: trimethylsilyl,
Pyr: pyrrolyl,    Indo: indolyl,
Vi: vinyl

The combinations of CA 1 and CA 2 may be, in addition to the above, those of a substituted cyclopentadienyl group and a substituted tetrahydroindenyl group, a substituted cyclopentadienyl group and a substituted benzoindenyl group, a substituted indenyl group and a substituted tetrahydroindenyl group, a substituted indenyl group and a substituted benzoindenyl group, a substituted tetrahydroindenyl group and a substituted benzoindenyl group, a substituted tetrahydroindenyl group and a substituted fluorenyl group, and a substituted benzoindenyl group and a substituted fluorenyl group.

The metallocene compounds of formula (1) wherein Z is —(R 1 )N—, —O—, —S— and —(R 1 )P—, respectively are represented by the following formulas (3a)-(3d). Concrete examples of the compounds of formula (3a) are shown in the attached Tables 20 and 21, by way of indicating concrete groups corresponding to each symbol using the above abbreviations.

The metallocene compounds of the present invention can be prepared by the following methods.

(a) A substituted cycloalkadiene anion represented by the following formula (4Aa)

(Ra) p (R 1 ) m (CA 1 ) − —  (4Aa)

wherein CA 1 , Ra, R 1 , p and m have respectively the meanings as defined above, is reacted with a binding agent represented by the following formula ( 5 A), at a molar ratio of 2:1,

X 2 —Y—X 2   (5A)

wherein Y has the meaning as defined above and X 2 represents a hydrogen atom or a halogen atom, said anion being prepared by reacting a substituted cycloalkadiene represented by the following formula (4A)

(Ra) p (R 1 ) m (CA 1 )H  (4A)

with a metal salt type base to effect an anionization; or a substituted cycloalkadiene anion represented by formula (4Aa) is reacted with any one of the compounds represented by the following formulas (5B) to (5F), at a molar ratio of 1:1,

X 2 —Y—(CA 2 )(R 1 ) n (Ra) q   (5B)

X 2 —Y—(R 1 )NH  (5C)

X 2 —Y—OH  (5D)

X 2 —Y—SH  (5E)

X 2 —Y—(R 1 )PH  (5F)

wherein Y, CA 2 , Ra, R 1 , n, q and X 2 have respectively the meanings as defined above, to form a compound represented by the following formula (6)

(Ra) p (R 1 ) m (CA 1 )—Y—Z 1   (6)

wherein Z 1 represents (CA 1 )(R 1 ) m (Ra) p , (CA 2 )(R 1 ) n (Ra) q , (R 1 )NH, —OH, —SH or (R 1 )PH.

(b) Subsequently, a dianion represented by the following formula (6A)

(Ra) p (R 1 ) m (CA 1 ) − —Y—Z − —  (6A)

wherein each symbol has the meaning as defined above, is reacted with a transition metal compound represented by the following formula (7)

(X 1 ) 2 —M—(X 3 ) 2   (7)

wherein M and X 1 have the meaning as defined above and X 3 represents hydrogen or a halogen atom, said dianion being prepared by reacting the compound represented by formula (6) with a metal salt type base to anionize each of the cycloalkadienyl ring and Z 1 , thus preparing the metallocene compound represented by formula (1).

The compound represented by formula (2A) can be prepared by reacting the substituted cycloalkadiene anion represented by formula (4Aa) with the binding agent represented by formula (5A) at a molar ratio of 2:1 to obtain a bis-substituted cyclopentadiene of formula (6) wherein Z 1 is (CA 1 )(R 1 ) m (Ra) p and subsequently conducting said (b) step.

The compounds represented by formula (5B) can be prepared by reacting a substituted or unsubstituted cycloalkadiene anion represented by the following formula (4Ba)

(Ra) q (R 1 ) n (CA 2 ) − —  (4Ba)

with a binding agent represented by formula ( 5 A) at a molar ratio of 1:1, said anion being prepared by reacting a substituted or unsubstituted cycloalkadiene represented by the following formula (4B)

(Ra) q (R 1 ) n (CA 2 )H  (4B)

with a metal salt type base to carry out an anionization. The compound of formula (SB) can produce the metallocene compounds of formula (2) wherein CA 1 and CA 2 are different each other.

The compounds represented by formula (5c): X 2 —Y—(R 1 )NH are secondary amines wherein Y is a hydrocarbon group, a silylene group, a germanium group or a stannyl group.

The compounds represented by formula (5d): X 2 —Y—OH are alcohols wherein Y is a hydrocarbon group, silanols wherein Y is a silylene group, germaniols wherein Y is a germanium group and stannyols wherein Y is a stannyl group.

The compounds represented by formula (5e): X 2 —Y—SH are thiols derived from the alcohols of formula (5) by replacing with —SH.

The compounds represented by formula (5f): X 2 —Y—(R 1 )PH are secondary phosphines wherein Y is as defined above.

In these compounds represented by formulas (5b)-(5f), X 2 is preferably a halogen atom.

The binding agents represented by formula (5A) include the compounds wherein Y is a hydrocarbon group, e.g., dichlorodimethylmethane, dichlorodiethylmethane, dichloro-di-n-propylmethane, dichloro-di-n-butylmethane, dichlorodiphenylmethane, dibromodimethylmethane, dibromodiethylmethane, dibromo-di-n-propylmethane, dibromo-di-n-butylmethane, dibromodiphenylmethane, dichlorotetramethylethane or dibromotetraethylethane; the compounds wherein Y is a silylene group, e.g., dichlorodimethylsilane, dichlorodiethylsilane, dichloro-di-n-propylsilane, dichloro-di-n-butylsilane, dichlorodiphenylsilane, dibromodimethylsilane, dibromodiethylsilane, dibromo-di-n-propylsilane, dibromo-di-n-butylsilane or dibromodiphenylsilane; the compounds wherein Y is a germanium group, e.g., dichlorogermaniumdimethyl, dichlorogermaniumdiethyl, dichlorogermanium-di-n-propyl, dichlorogermanium-di-n-butyl, dichlorogermaniumdiphenyl, dibromogermaniumdimethyl, dibromogermaniumdiethyl, dibromogermanium-di-n-propyl, dibromogermanium-di-n-butyl or dibromogermaniumdiphenyl; and similar compounds wherein Y is a stannyl group.

The substituted cycloalkadienes represented by said formulas (4A) and (4B) are substituted cyclopentadienes, substituted indenes, substituted tetrahydroindenes, substituted benzoindenes or substituted fluorenes wherein a hydrogen atom on the cycloalkadiene ring is substituted by a heteroaromatic group Ra and/or a substituent R 1 .

These substituted cycloalkadienes can be prepared by reacting a heteroaromatic anion anionized by reacting a heteroaromatic compound with or without a halogen atom at the position bonding to the cycloalkadiene ring with a metal salt type base, with a cycloalken-one wherein a hydrogen atom on the cycloalkadiene ring to be substituted by the heteroaromatic group is substituted by an oxygen atom, thus converting into a keto form.

The transition metal compounds represented by formula (7) are metal tetrahalide compounds, e.g., titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrafluoride, titanium trichloride, titanium tribromide, titanium triiodide, titanium trifluoride, zirconium tetrachloride, zirconium tetrabromide, zirconium tetraiodide, zirconium tetrafluoride, hafnium tetrachloride, hafnium tetrabromide, hafnium tetraiodide or hafnium tetrafluoride; and metal tri- or di-halide compounds wherein up to two of the halogen atoms are substituted by said hydrocarbon group, halogenated hydrocarbon group or silyl group, preferably metal tetrahalide compounds.

In the above-described processes, the anionization of substituted cycloalkadienes sustitued by the heteroaromatic group and the dianionization of the bis- or di-substituted cycloalkadienes mean the anionization of each 5-membered ring, i.e., cyclopentadiene ring. The former permits a linkage of two molecules by reaction with a binding agent subsequent to anionization, and the latter permits an intramolecular linkage for ring closure by is reaction with a transition metal compound subsequent to dianionization.

The metal salt type bases used in the anionization of the cyclopentadiene and aromatic rings in each step of the above-mentioned processes, include, for example, methyllithium, n-butyllithium, t-butyllithium, phenyllithium, lithium hydride, sodium hydride, potassium hydride, calcium hydride, lithium diisopropylamide, t-butyloxypotassium, methylmagnesium iodide, ethylmagnesium iodide, phenylmagnesium bromide and t-butylmagnesium bromide.

The anionization reaction of substituted cycloalkadienes substituted by the heteroaromatic group and bis- or di-substituted cycloalkadienes can be carried out with said metal salt type base in the presence of an amine compound which includes primary amines, e.g., methylamine, ethylamine, n-propyl-amine, isopropylamine, n-butylamine, tert-butylamine, aniline or ethylenediamine; secondary amines, e.g. dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-tert-butylamine, pyrrolidine, hexamethyldisilazane or diphenylamine; and tertiary amines, e.g. trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, tri-tert-butylamine, triphenylamine, N,N-dimethylaniline, N,N,N′,N′-tetramethylethylenediamine, N-methylpyrrolidine or 4-dimethylaminopyridine.

Each of the above-mentioned reactions is usually carried out in an organic solvent at a reaction temperature between not lower than −100° C. and not higher than a boiling point of the solvent, preferably in the range of −70° C. to 100° C.

The solvents used in the reaction can be used without any limitation, if they are not reactive to the above starting compounds and reaction products and do not decompose them. Preferably, ethers, halogenated hydrocarbons or aromatic compounds are used. For ethers, preferable are relatively low-molecular ethers such as diethylether, diisopropylether and tetrahydrofuran, dimethoxyethane. Dichloromethane is preferable for halogenated hydrocarbons. For aromatic compounds, preferable are toluene, anisol and xylene. Further, a mixed solvent of these two or more compounds can be used.

The synthesis of the metallocene compounds represented by formula (2A) is mentioned below.

The bis-substituted cycloalkadiene prepared by reacting the substituted cycloalkadiene anion represented by formula (4Aa) with the binding agent represented by formula (5A) is generally formed as a mixture of a racemic form consisting of a compound having a steric structure unsymmetrical with respect to Y and the enantiomer thereof and a compound having a steric structure symmetrical with respect to Y.

Usually, the resultant reaction mixture to which water has been added, is allowed to stand to separate into an organic layer and a water layer, thus obtaining the bis-substituted cycloalkadiene as an organic layer. The bis-substituted cycloalkadiene can be used as it is in the form of a resulting solution for the subsequent step, but usually used after separation from the solution. For the purpose of separating the bis-substituted cycloalkadiene from the solution, the method of distilling off the solvent can be employed, for example. The separated cycloalkadiene is further purified by recrystallization, distillation, column chromatography or the like, and may be further separated into the racemic and meso forms, and each form may be further purified and used for the subsequent step.

The bis-substituted cycloalkadiene as prepared above is reacted with a metal salt type base to anionize each 5-membered ring, thereby forming the dianion represented by formula (4Ba), and then this bis-substituted cycloalkadiene dianion is reacted with the transition metal compound represented by formula (7) to achieve an intramolecular linkage for ring closure, thus forming a mixture of the racemic and meso forms of the metallocene compound represented by formula (2A).

Finally, each of the racemic and meso forms of the metallocene compounds is isolated from the above-mentioned reaction solution in the usual way and purified to obtain the racemic and meso metallocene compounds. Isolation and purification of the racemic and meso metallocene compounds can be effected by distilling the solvent off, if necessary, extraction with a suitable solvent, adsorption, filtration, recrystallization or the like. Usually, each compound is crystallized out by utilizing the difference in solubility of the compound in a solvent and then purified by recrystallization or the like.

The scheme for the synthesis of dimethylsilylenebis[2-(2-furyl)-3,5-dimethylcyclopentadienyl]-zirconium dichloride (Compound No. 94 in the attached Table 3), represented by formula (2A) wherein CA 1 is a cyclopentadienyl group substituted by furyl and two methyl groups, Y is dimethylsilylene, M is zirconium and X 1 is chlorine, is shown in the attached FIG. 3 .

The catalysts for olefin polymerization of the present invention contain the metallocene compound represented by formula (1) as a principal component. Preferably, the metallocene compounds represented by formula (2), and more preferably, the metallocene compounds represented by formula (2A) are used as the principal component.

The metallocene compounds represented by formula (2A) may be the racemic or meso forms isolated in said processes for the preparation, or may be those separated from the solution and purified in the form of the mixture without isolation of each form.

Other components constituting the catalyst for polymerization of olefin in combination with said metallocene compounds can include one or more compounds which are generally used in the polyolefin polymerization, selected from, for example, an aluminoxane, an ionic compound which can react with a metallocene compound to form an ionic complex and Lewis acid.

The aluminoxane is an organoaluminum compound represented by the following formula (8) or (9):

in which R 3 is a hydrocarbon group of 1-20 carbons, preferably 1-4 carbons and concretely represents methyl, ethyl, propyl, isopropyl, butyl or isobutyl, R 3 may be identical or different, and r is an integer of 1 to 1000, but said compound may be a mixture of aluminoxanes having different r values.

The ionic compounds are salts of cationic and anionic compounds. An anion has an action to cationize the metallocene compound by reaction therewith and to stabilize the cation species in the metallocene compound by formation of an ion pair. The anions include those of organoboron compounds, organoaluminum compounds or the like. The cations include metallic cations, organometallic cations, carbonium cations, tropium cations, oxonium cations, sulfonium cations, phosphonium cations and ammonium cations. Of these, preferable are ionic compounds containing a boron atom as an anion. Examples of those compounds include N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate and trityltetrakis-(pentafluorophenyl)borate.

For Lewis acid, preferable is a boron-containing Lewis acid. Examples thereof include tri(n-butyl)boron, triphenyl boron, tris[3,5-bis(trifluoromethyl)-phenyl]boron, tris[(4-fluoromethyl)phenyl]boron, tris(3,5-difluorophenyl)boron, tris(2,4,6-trifluorophenyl)boron and tris(pentafluorophenyl)boron.

In addition to the above, known ionic compounds which can react with the metallocene compounds to form the ionic complexes and Lewis acids can be also used.

The proportion of the metallocene compounds and these catalyst components used is in such a range that the Al atom in the aluminoxane is 1-50,000 mols, preferably 50-20,000 mols per mol of the transition metal atom in the metallocene compound, when the aluminoxane is used as a catalyst component. When the ionic compound or Lewis acid is used as a catalyst component, the ionic compound or Lewis acid is in the range of 0.01-2,000 mols, preferably 0.1-500 mols, per mol of the transition metal atom in the metallocene compound.

In the present invention, another embodiment of the catalyst for olefin polymerization is composed of said metallocene compound, said aluminoxane and a support in the form of finely divided particles. Usually, each of the metallocene compound and the aluminoxane or a reaction product of the metallocene compound and the aluminoxane is used by supporting it on said support. The supports employed are finely divided inorganic or organic solid particles in the form of granules or spheres, the particle size of which is in the range of 5-300 μm, preferably 10-200 μm.

For the inorganic supports, preferable are metal oxides, e.g., SiO 2 , Al 2 O 3 , MgO, TiO 2 and ZnO, or the mixture thereof. The supports containing as a principal component at least one selected from the group consisting of SiO 2 , Al 2 O 3 and MgO are especially preferable. More specifically, inorganic compounds can include SiO 2 , Al 2 O 3 , MgO, SiO 2 —Al 2 O 3 , SiO 2 —MgO, SiO 2 —TiO 2 and SiO 2 —Al 2 O 3 —MgO. These inorganic oxide supports are usually calcined at a temperature of 100-1000° C. for 1-40 hrs.

The organic supports can include the polymers or copolymers of α-olefins of 2-12 carbons such as ethylene, propylene, 1-butene or 4-methyl-1-pentene, and the polymers or copolymers of styrene or styrene derivatives.

The process for the production of an olefin polymer according to the present invention comprises polymerizing an olefin in the presence of said catalyst for olefin polymerization. Preferably, an olefin is polymerized in the presence of the catalyst for olefin polymerization formed from metallocene compounds, aluminoxanes and said supports as well as organoaluminum compounds.

The term “polymerization” in the present specification is used in the sense to include a homopolymerization and copolymerization. The term “olefin polymer” includes a homopolymer of one olefin and a copolymer of two or more olefins.

In the present invention, the polymerizable olefins include straight-chain a-olefins, e.g., ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene or 1-eicosene; branched-chain α-olefins, e.g., 3-methyl-l-butene, 4-methyl-1-pentene or 2-methyl-l-pentene; and the mixture of these two or more species.

The processes for the production of the olefin polymer according to the present invention can produce not only homopolymers of said olefins, but also random copolymers comprising, e.g., a combination of two components such as ethylene/propylene, propylene/1-butene, a combination of three components such as ethylene/propylene/1-butene, block copolymers by varying kinds of olefins which feed in a multistage polymerization.

The polymerization of a cyclic olefin, a diene, a styrene and the derivatives thereof and other polymerizable monomers having a double bond or the copolymerization with an α-olefin can be carried out by use of the above-mentioned processes for the production of olefin polymers.

The polymerizable cyclic olefins include, for example, cyclobutene, cyclopentene, cyclohexene, cycloheptene, norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, phenylnorbornene and indanylnorbornene. The dienes include, for example, cyclic dienes, e.g., 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-propylidene-5-norbornene, dicyclopentadiene or 5-vinyl-2-norbornene; and acyclic dienes, e.g., 1,3-butadiene, isoprene, 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 1,7-octadiene, 6-methyl-1,7-octadiene, 7-methyl-1,6-octadiene, 1,8-nonadiene or 1,9-decadiene. The styrenes and their derivatives include, for example, styrene, p-chlorostyrene, p-methylstyrene, p-tert-butylstyrene, α-methylstyrene and vinylnaphthalene. Other polymerizable monomers having a double bond include, for example, vinylcyclohexane, vinyl chloride, 4-trimethylsiloxy-1,6-heptadiene, 5-(N,N-diisopropylamino)-1-pentene, methylmethacrylate and ethylacrylate.

The organoaluminum compounds coexistent with the olefin polymerization catalyst in the olefin polymerization system are triethylaluminum, triisopropylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, diisobutylaluminum hydride or the like and the mixture thereof, and triethylaluminum and triisobutylaluminum are preferably used.

In the processes for the production of olefin polymers according to the present invention, both of a liquid-phase polymerization and a vapor-phase polymerization can be employed as a process for the polymerization of olefins. In the liquid-phase polymerization, an inert hydrocarbon may be a solvent, and further a liquid olefin itself such as a liquid propylene and a liquid 1-butene can be used as a solvent. The solvents for polymerization include an aromatic hydrocarbon, e.g., benzene, toluene, ethylbenzene or xylene; an aliphatic hydrocarbon, e.g., butane, isobutane, pentane, hexane, heptane, octane, decane, dodecane, hexadecane or octadecane; an alicyclic hydrocarbon, e.g., cyclopentane, methylcyclopentane, cyclohexane or cyclooctane; and a petroleum cut, e.g., gasoline, kerosene or gas oil.

The polymerization process may employ either of batch-wise, semi-continuous and continuous methods. Further, the polymerization may be carried out in two or more stages divided by changing the reaction conditions.

The metallocene compounds used in the polymerization process, particularly the metallocene compounds of formula (2A), may be either of an isolated racemic or meso form, or the separated and purified mixture thereof. In particular, the isolated racemic form achieves an extremely great effect in making the molecular weight of the produced polypropylene higher.

The concentration of the metallocene compound within the polymerization reaction system, with no particular limitation thereon, is preferably in the range of 10 −2 -10 −10 mol/l based on the transition metal.

The pressure of olefins in the polymerization reaction system, with no particular limitation thereon, is preferably in the range of normal pressure to 50 kg/cm 2 . Further, the polymerization temperature, with no particular limitation thereon, is usually in the range of −50 to 250° C., preferably −30 to 100° C. The regulation of the molecular weight upon the polymerization can be effected by known means, for example, choice of the temperature or introduction of hydrogen.

The olefin polymers produced by the above-mentioned processes are provided for various forming or molding materials, through conventional process steps such as the deactivation treatment of catalyst, the treatment for catalyst residue, drying or the like.

EXAMPLE

Example 1

Synthesis of dimethylsilylenebis[3-(2-furyl)-2,5-dimethylcyclopentadienyl]zirconium dichloride (Compound No. 254)

(a1) Synthesis of 1-(2-furyl)-2,4-dimethylcyclopentadiene

A 500 ml glass reaction vessel was charged with 9.4 g (0.14 mol) of furan and 150 ml of tetrahydrofuran (THF) and cooled to −20° C. on a dry ice/methanol bath. To the mixture were added dropwise 90 ml (0.14 mmol) of an n-butyllithium/hexane solution of 1.54 mol/l. After the addition was completed, the mixture was raised to room temperature and stirred for 6 hrs. The mixture was again cooled to −20° C. on a dry ice/methanol bath and 30 ml of a THF solution containing 15.2 g (0.14 mol) of 2,4-dimethylcyclopenten-1-one were added dropwise. After the addition was completed, the mixture was raised to room temperature and stirred for 16 hrs.

The reaction solution was cooled to −20° C. on a dry ice/methanol bath and 10 ml of 2N-hydrochloric acid were added dropwise. This reaction solution was transferred into a separatory funnel and washed with brine until it was neutral. Anhydrous sodium sulfate was added and the solution was allowed to stand overnight and dried. Anhydrous sodium sulfate was filtered off and the solvent was distilled off under reduced pressure. Purification of the residue with a silica gel column gave 20.3 g (92% yield) of a yellow liquid of 1-(2-furyl)-2,4-dimethylcyclopentadiene. The structure was identified by NMR.

(a2) Synthesis of dimethylbis[3-(2-furyl)-2,5-dimethylcyclopentadienyl]silane

A 500 ml glass reaction vessel was charged with 20.3 g (0.13 mol) of 1-(2-furyl)-2,4-dimethylcyclopentadiene and 130 ml of THF and cooled to −30° C. on a dry ice/methanol bath. To the mixture were added dropwise 85 ml (0.13 mmol) of an n-butyllithium/hexane solution of 1.54 mol/l. After the addition was completed, the mixture was raised to room temperature and stirred for 16 hrs. The mixture was again cooled to −30° C. on a dry ice/methanol bath and 30 ml of a THF solution containing 8.2 g (0.064 mol) of dimethyl dichlorosilane were added dropwise. After the addition was completed, the mixture was raised to room temperature and stirred for 16 hrs.

To the reaction solution was added distilled water. This reaction solution was transferred into a separatory funnel and washed with brine until it was neutral. Anhydrous sodium sulfate was added and the solution was allowed to stand overnight and dried. Anhydrous sodium sulfate was filtered off and the solvent was distilled off under reduced pressure. Purification of the residue with a silica gel column gave 7.7 g (33% yield) of dimethylbis[3-(2-furyl)-2,5-dimethylcyclopentadienyl]-silane as a yellow liquid. The structure was identified by NMR.

(b) Synthesis of dimethylsilylenebis[3-(2-furyl)-2,5-dimethylcyclopentadienyl]zirconium dichloride

A 100 ml glass reaction vessel was charged with 2.0 g (0.050 mol) of potassium hydride (KH) and 40 ml of THF and cooled to −70° C. on a dry ice/methanol bath. To the mixture were added dropwise 40 ml of a THF solution containing 7.7 g (0.021 mol) of dimethylbis[3-(2-furyl)-2,5-dimethylcyclopentadienyl]silane as synthesized above. After the addition was completed, the mixture was returned to room temperature and stirred for 16 hrs. The reaction solution was allowed to stand and a supernatant solution was transferred into a 100 ml glass reaction vessel. The solvent in the supernatant solution was distilled off under reduced pressure, 15 ml of dichloromethane were added, and the reaction solution was solidified with liquid nitrogen, to which were added 45 ml of a dichloromethane suspension containing 6.2 g (0.027 mol) of tetrachlorozirconium. Subsequently, the mixture was raised to room temperature and stirred for 16 hrs. A part of the reaction solution was withdrawn and determined by 1 H-NMR, by which it was found to be a mixture of a racemic form/meso form (molar ratio=58/42).

The solvent was distilled off under reduced pressure, the residue was extracted with hexane and recrystallized from toluene/hexane to obtain 90 mg (0.8% yield) of dimethylsilylenebis[3-(2-furyl)-2,5-dimethylcyclopentadienyl]zirconium dichloride (racemic form/meso form (molar ratio)=49/51).

1 H-NMR (CDCl 3 ) Racemic form δ: 1.04 (s, 6H), δ: 2.24 (s, 6H), δ: 2.31 (s, 6H), δ: 6.47 (m, 4H), δ: 7.06 (5, 2H), δ: 7.44 (dd, 2H),

Meso form δ: 1.04 (s, 3H), δ: 1.06 (s, 3H), δ: 2.23 (s, 6H), δ: 2.35 (s, 6H), δ: 6.42 (d, 4H), δ: 6.94 (s, 2H), δ: 7.41 (t, 2H).

Example 2

Synthesis of dimethylsilylenebis[2-(2-furyl)-3,5-dimethylcyclopentadienyl]zirconium dichloride (Compound No. 94)

(b) Synthesis of dimethylsilylenebis[2-(2-furyl)-3,5-dimethylcyclopentadienyl]zirconium dichloride

A 100 ml glass reaction vessel was charged with 3.98 g (0.011 mol) of dimethylbis[2-(2-furyl)-4,5-dimethylcyclopentadienyl]silane synthesized by a similar procedure as in step (a) of Example 1 and 30 ml of THF, and cooled to −30° C. on a dry ice/methanol bath. To the mixture were added dropwise 15 ml (0.023 mmol) of an n-butyllithium/hexane solution of 1.52 mol/l. After the addition was completed, the mixture was raised to room temperature and stirred for 16 hrs. The solvent in the reaction solution was distilled off under reduced pressure, 10 ml of dichloromethane were added, and the reaction solution was solidified with liquid nitrogen, to which were added 30 ml of a dichloromethane suspension containing 2.5 g (0.011 mol) of tetrachloro-zirconium. Subsequently, the mixture was raised to room temperature and stirred for 16 hrs. A part of the reaction solution was withdrawn and determined by 1 H-NMR, by which it was found to be a racemic form/meso form (molar ratio=77/23).

The solvent was distilled off under reduced pressure and the residue was extracted with hexane to afford 2.3 g of dimethylsilylenebis[2-(2-furyl)-3,5-dimethylcyclopentadienyl]zirconium dichloride (racemic form/meso form (molar ratio)=78/22, yield 40.6%). Recrystallization gave 140 mg of the racemic form (purity 99% or more).

The ORTEP diagram of the resultant rac-dimethylsilylenebis[2-(2-furyl)-3,5-dimethylcyclopentadienyl]zirconium dichloride is shown in FIG. 2 .

1 H-NMR (CDCl 3 )

Racemic form δ: 0.62 (s, 6H), δ: 1.66 (s, 6H), δ: 2.27 (s, 6H), δ: 6.38 (dd, 2H), δ: 6.44 (dd, 2H), δ: 6.59 (s, 2H), δ: 7.42 (dd, 2H)

Meso form δ: 0.18 (s, 3H), δ: 1.06 (s, 3H), δ: 2.26 (s, 6H), δ: 2.36 (s, 6H), δ: 5.94 (dd, 2H), δ: 6.14 (dd, 2H), δ: 6.50 (s, 2H), δ: 7.14 (dd, 2H).

Example 3

Synthesis of dimethylsilylenebis[2-(2-furyl)-4,5-dimethylcyclopentadienyl]zirconium dichloride (Compound No. 95)

(a1) Synthesis of 1-(2-furyl)-3,4-dimethylcyclopentadiene

A 1 l glass reaction vessel was charged with 21.0 g (0.31 mol) of furan and 400 ml of diethyl ether and cooled to −30° C. on a dry ice/methanol bath. To the mixture were added dropwise 200 ml (0.31 mmol) of an n-butyllithium/hexane solution of 1.53 mol/l. After the addition was completed, the mixture was raised to room temperature and stirred for 4 hrs. The mixture was again cooled to −30° C. on a dry ice/methanol bath and 100 ml of a diethyl ether solution containing 33.0 g (0.30 mol) of 3,4-dimethylcyclopenten-1-one were added dropwise. After the addition was completed, the mixture was returned to room temperature and stirred for 16 hrs.

To the reaction solution was added distilled water, this solution was transferred into a separatory funnel and washed three times with brine. Subsequently, the solution was shaken twice with 50 ml of 5N hydrochloric acid and washed with brine until it was neutral. Anhydrous sodium sulfate was added and the solution was allowed to stand overnight and dried. Anhydrous sodium sulfate was filtered off and the solvent was distilled off under reduced pressure. Purification of the residue with a silica gel column gave 24.6 g (51% yield) of 1-(2-furyl)-3,4-dimethylcyclopentadiene as a red liquid. The structure was identified by NMR.

(a2) Synthesis of dimethylbis[2-(2-furyl)-4,5-dimethylcyclopentadienyl]silane

A 1 l glass reaction vessel was charged with 24.3 g (0.15 mol) of 1-(2-furyl)-3,4-dimethylcyclopentadiene and 300 ml of THF and cooled to −30° C. on a dry ice/methanol bath. To the mixture were added dropwise 100 ml (0.15 mmol) of a n-butyllithium/hexane solution of 1.52 mol/l. After the addition was completed, the mixture was raised to room temperature and stirred for 3 hrs. The mixture was again cooled to −30° C. on a dry ice/methanol bath and 50 ml of of a THF solution containing 9.8 g (0.076 mol) of dimethyl dichlorosilane were added dropwise. After the addition was completed, the mixture was raised to room temperature and stirred for 16 hrs.

To the reaction solution was added distilled water. This reaction solution was transferred into a separatory funnel and washed with brine until it was neutral. Anhydrous sodium sulfate was added and the solution was allowed to stand overnight and dried. Anhydrous sodium sulfate was filtered off and the solvent was distilled off under reduced pressure. Purification of the residue with a silica gel column and recrystallization with toluene/hexane gave 19.4 g (68% yield) of dimethylbis-[2-(2-furyl)-4,5-dimethylcyclopentadienyl]silane as yellow crystals.

(b) Synthesis of dimethylsilylenebis[2-(2-furyl)-4,5-dimethylcyclopentadienyl]zirconium dichloride

A 500 ml glass reaction vessel was charged with 10.0 g (0.027 mol) of dimethylbis[2-(2-furyl)-4,5-dimethylcyclopentadienyl]silane and 200 ml of THF and cooled to −30° C. on a dry ice/methanol bath. To the mixture was added dropwise 35 ml (0.053 mmol) of an n-butyllithium/hexane solution of 1.52 mol/l. After the addition was completed, the mixture was raised to room temperature and stirred for 16 hrs. The solvent was distilled off under reduced pressure, 200 ml of toluene were added, and the solution was cooled to −70° C. on a dry ice/methanol bath. To the solution, 6.2 g (0.027 mol) of tetrachlorozirconium were added as it was solid. Subsequently, the mixture was raised to room temperature, stirred for 16 hrs. and heated at 80° C. for 4 hrs. A part of the reaction solution was withdrawn and determined by 1 H-NMR, by which it was found to be a racemic form/meso form (molar ratio=61/39).

The solvent was distilled off under reduced pressure and the residue was extracted with hexane to afford 2.5 g of dimethylsilylenebis[2-(2-furyl)-4,5-dimethylcyclopentadienyl]zirconium dichloride (racemic form/meso form=58/42, 17.5% yield) as yellow powders. Further recrystallization gave 120 mg of the racemic form (purity 99% or more) and 170 mg of the meso form (purity 99% or more).

1 H-NMR (CDCl 3 ) (See, FIG. 1 ) Racemic form δ: 0.79 (s, 6H), δ: 1.45 (s, 6H), δ: 2.19 (s, 6H), δ: 6.41 (dd, 2H), δ: 6.55 (dd, 2H), δ: 6.72 (s, 2H), δ: 7.39 (dd, 2H)

Meso form δ: 0.62 (s, 3H), δ: 1.00 (s, 3H), δ: 2.02 (s, 6H), δ: 2.29 (s, 6H), δ: 6.12 (d, 4H), δ: 6.65 (d, 2H), δ: 7.13 (t, 2H).

Example 4

Synthesis of dimethylsilylenebis[3-(2-thienyl)-2,5-dimethylcyclopentadienyl]zirconium dichloride (Compound No. 274)

(a1) Synthesis of 1-(2-thienyl)-2,4-dimethylcyclopentadiene

A 200 ml glass reaction vessel was charged with 5.3 g (0.063 mol) of thiophene and 60 ml of THF and cooled to −10° C. on a dry ice/methanol bath. To the mixture were added dropwise 41 ml (0.064 mmol) of a n-butyllithium/hexane solution of 1.56 mol/l. After the addition was completed, the mixture was raised to room temperature and stirred for one hour. The mixture was again cooled to −20° C. on a dry ice/methanol bath and 30 ml of a THF solution containing 7.0 g (0.064 mol) of 2,4-dimethylcyclopenten-1-one were added dropwise. After the addition was completed, the mixture was raised to room temperature and stirred for 16 hrs.

The reaction solution was cooled to −20° C. on a dry ice/methanol bath and 7 ml of 2N-hydrochloric acid were added dropwise. This reaction solution was transferred into a separatory funnel and washed with brine until it was neutral. Anhydrous sodium sulfate was added and the solution was allowed to stand overnight and dried. Anhydrous sodium sulfate was filtered off and the solvent was distilled off under reduced pressure. Purification of the residue with a silica gel column gave 9.7 g (87% yield) of a yellow-orange liquid of 1-(2-thienyl)-2,4-dimethylcyclopentadiene. The structure was identified by NMR.

(a2) Synthesis of dimethylbis[3-(2-thienyl)-2,5-dimethylcyclopentadienyl]silane

A 100 ml glass reaction vessel was charged with 3.53 g (0.020 mol) of 1-(2-thienyl)-2,4-dimethylcyclopentadiene as synthesized above and 40 ml of THF and cooled to −30° C. on a dry ice/methanol bath. To the mixture were added dropwise 14 ml (0.022 mmol) of an n-butyllithium/hexane solution of 1.56 mol/l. After the addition was completed, the mixture was raised to room temperature and stirred for 16 hrs. The mixture was again cooled to −30° C. on a dry ice/methanol bath and 20 ml of a THF solution containing 1.3 g (0.010 mol) of dimethyl dichlorosilane were added dropwise. After the addition was completed, the mixture was raised to room temperature and stirred for 16 hrs.

To the reaction solution was added distilled water. This reaction solution was transferred into a separatory funnel and washed with brine until it was neutral. Anhydrous sodium sulfate was added and the solution was allowed to stand overnight and dried. Anhydrous sodium sulfate was filtered off and the solvent was distilled off under reduced pressure. Purification of the residue with a silica gel column gave 1.3 g (16% yield) of a yellow liquid of dimethylbis[3-(2-thienyl)-2,5-dimethylcyclopentadienyl]silane. The structure was identified by NMR.

(b) Synthesis of dimethylsilylenebis[3-(2-thienyl)-2,5-dimethylcyclopentadienyl]zirconium dichloride

A 100 ml glass reaction vessel was charged with 0.4 g (0.010 mol) of potassium hydride (KH) and 30 ml of THF and cooled to −70° C. on a dry ice/methanol bath. To the mixture were added dropwise 20 ml of a THF solution containing 1.2 g (0.0030 mol) of dimethylbis[3-(2-thienyl)-2,5-dimethylcyclopentadienyl]silane as synthesized above. After the addition was completed, the mixture was raised to room temperature and stirred for 16 hrs. The reaction solution was allowed to stand and a supernatant solution was transferred into a 100 ml glass reaction vessel. The solvent in the supernatant solution was distilled off under reduced pressure, 15 ml of dichloromethane were added, and the reaction solution was solidified with liquid nitrogen, to which were added 45 ml of a dichloromethane suspension containing 0.7 g (0.0031 mol) of tetrachlorozirconium. Subsequently, the mixture was raised to room temperature and stirred for 16 hrs. A part of the reaction solution was withdrawn and determined by 1 H-NMR, by which it was found to be a racemic form/meso form (molar ratio=55/45).

The solvent was distilled off under reduced pressure, the residue was extracted with hexane and recrystallized with toluene/hexane to obtain 30 mg (2% yield) as yellow crystals of dimethylsilylenebis[3-(2-thienyl)-2,5-dimethylcyclopentadienyl)zirconium dichloride (racemic form/meso form (molar ratio)=60/40).

1 H-NMR (CDCl 3 ) Racemic form δ: 1.05 (s, 6H), δ: 2.25 (s, 6H), δ: 2.35 (s, 6H), δ: 6.99 (s, 2H), δ: 7.09 (dd, 2H), δ: 7.20 (dd, 2H), δ: 7.30 (dd, 2H)

Meso form δ: 1.05 (s, 3H), δ: 1.06 (s, 3H), δ: 2.26 (s, 6H), δ: 2.36 (s, 6H), δ: 6.87 (s, 2H), δ: 7.05 (dd, 2H), δ: 7.19 (dd, 2H), δ: 7.26 (dd, 2H).

Example 5

Synthesis of dimethylsilylenebis[2-(2-furyl)-indenyl]-zirconium dichloride (Compound No. 424)

(a1) Synthesis of 2-(2-furyl)-indene

A 500 ml glass reaction vessel was charged with 4.7 g (0.069 mol) of furan and 100 ml of THF and cooled to −50° C. on a dry ice/methanol bath. To the mixture were added dropwise 48 ml (0.073 mmol) of an n-butyllithium/hexane solution of 1.52 mol/l. After the addition was completed, the mixture was raised to room temperature and stirred for 3 hrs. The mixture was again cooled to −30° C. on a dry ice/methanol bath and 100 ml of a THF solution containing 9.1 g (0.069 mol) of 2-indanone were added dropwise. After the addition was completed, the mixture was raised to room temperature and stirred for 16 hrs.

The reaction solution was cooled to −20° C. on a dry ice/methanol bath and 10 ml of 2N-hydrochloric acid were added dropwise. This reaction solution was transferred into a separatory funnel and washed with brine until it was neutral. Anhydrous sodium sulfate was added and the solution was allowed to stand overnight and dried. Anhydrous sodium sulfate was filtered off and the solvent was distilled off under reduced pressure. Purification of the residue with a silica gel column gave 3.2 g (25% yield) of 2-(2-furyl)-indene as colorless crystals. The structure was identified by NMR.

(a2) Synthesis of dimethylbis[2-(2-furyl)-indenyl]silane

A 200 ml glass reaction vessel was charged with 1.3 g (0.0070 mol) of 2-(2-furyl)-indene as synthesized above, 0.09 g (0.001 mol) of copper cyanide and 30 ml of THF and cooled to −50° C. on a dry ice/methanol bath. To the mixture were added dropwise 5.2 ml (0.0079 mmol) of an n-butyllithium/hexane solution of 1.52 mol/l. After the addition was completed, the mixture was raised to room temperature and stirred for 16 hrs. The mixture was again cooled to −50° C. on a dry ice/methanol bath and 20 ml of THF solution containing 0.5 g (0.0039 mol) of dimethyl dichlorosilane were added dropwise. After the addition was completed, the mixture was raised to room temperature and stirred for 16 hrs.

To the reaction solution was added distilled water. This reaction solution was transferred into a separatory funnel and washed with brine until it was neutral. Anhydrous sodium sulfate was added and the solution was allowed to stand overnight and dried. Anhydrous sodium sulfate was filtered off and the solvent was distilled off under reduced pressure. Purification of the residue with a silica gel column gave 1.1 g (72% yield) of dimethylbis[2-(2-furyl)-indenyl]silane as light green crystals.

(b) Synthesis of dimethylsilylenebis[2-(2-furyl)-indenyl]zirconium dichloride

A 100 ml glass reaction vessel was charged with 1.1 g (0.0025 mol) of dimethylbis[2-(2-furyl)-indenyl]silane as synthesized above and 30 ml of THF and cooled to −50° C. on a dry ice/methanol bath. To the mixture were added dropwise 3.6 ml (0.0055 mmol) of an n-butyllithium/hexane solution of 1.52 mol/l. After the addition was completed, the mixture was raised to room temperature and stirred for 16 hrs. The solvent in the reaction solution was distilled off under reduced pressure, 10 ml of dichloromethane were added, and the reaction solution was solidified with liquid nitrogen, to which were added 30 ml of a dichloromethane suspension containing 0.6 g (0.0026 mol) of tetrachloro-zirconium. Subsequently, the mixture was raised to room temperature and stirred for 16 hrs. A part of the reaction solution was withdrawn and determined by 1 H-NMR, by which it was found to be dimethylsilylenebis[2-(2-furyl)-indenyl]-zirconium dichloride (racemic form/meso form(molar ratio=75/25).

The solvent was distilled off under reduced pressure, the residue was extracted with toluene and recrystallized with toluene to obtain 140 mg (10% yield) of a racemic form (purity 99% or more) of dimethylsilylenebis-[2-(2-furyl)-indenyl)zirconium dichloride.

1 H-NMR (CDCl 3 ) Racemic form δ: 1.11 (s, 6H), δ: 6.41 (dd, 2H), δ: 6.48 (dd, 2H), δ: 6.72 (m, 2H), δ: 6.89 (m, 2H), δ: 6.97 (s, 2H), δ: 7.33 (m, 2H), δ: 7.52 (dd, 2H), δ: 7.55 (m, 2H).

Example 6

Polymerization of Propylene

A SUS autoclave was charged with 1 liter of toluene and a toluene solution of methylaluminoxane (MMAO3A, manufactured by Toso-Aczo Co. Ltd.) in an amount equivalent to Al/Zr (molar ratio)=10,000, to which was added separately each solution containing in 3 ml of a toluene solution, 1.35×10 −6 mol of the metallocene compound of Compound No. 254 (racemic form/meso form (molar ratio)=49/51) synthesized in Example 1, 0.62×10 −6 mol of the metallocene compound of Compound No. 94 (racemic form 99%) synthesized in Example 2, 0.55×10 −6 mol of the metallocene compound of Compound No. 95 (racemic form 99%) synthesized in Example 3, 1.61×10 −6 mol of the metallocene compound of Compound No. 274 (racemic form/meso form (molar ratio)=60/40) synthesized in Example 4, and 0.30 x 10-6 mol of the metallocene compound of Compound No. 424 (racemic form 99%) synthesized in Example 5, respectively, and each mixture was heated to 30° C. Into the autoclave was introduced propylene at a pressure of 0.3 MPaG and a polymerization was carried out for one hour. After the polymerization was completed, a polymer was filtered and a catalyst component was decomposed with 1 liter of hydrochloric acidic methanol. Subsequently, 1e filtration, washing and drying were carried out in order to obtain a polypropylene in an amount of 43.1 g, 42.7 g, 20.9 g, 33.6 g and 4.6 g, respectively.

The analytical values for the resultant polypropylene are shown in Table 1.

Example 7

Synthesis of dimethylsilylenebis[2-(2-thienyl)-4,5dimethylcyclopentadienyl]zirconium dichloride

(a1) Synthesis of 1-(2-thienyl)-3,4-dimethylcyclopentadiene

A 1 l glass reaction vessel was charged with 25.3 g (0.30 mol) of thiophene and 350 ml of THF and the mixture was cooled to −70° C. on a dry ice/methanol bath. To the mixture were added dropwise 200 ml (0.30 mol) of an n-butyllithium/hexane solution of 1.52 mol/l. After the addition was completed, the mixture was raised to room temperature and stirred for 16 hrs. The mixture was again cooled to −30° C. on a dry ice/methanol bath and 100 ml of a THF solution containing 33.0 g (0.30 mol) of 3,4-dimethylcyclopenten-1-one were added dropwise. After the addition was completed, the mixture was raised to room temperature and stirred for 16 hrs.

To the reaction solution was added distilled water. This solution was transferred into a separatory funnel and washed three times with brine. Subsequently, the solution was shaken twice with 50 ml of 5N hydrochloric acid and washed with brine until it was neutral. Anhydrous sodium sulfate was added and the solution was allowed to stand overnight and dried. Anhydrous sodium sulfate was filtered off and the solvent was distilled off under reduced pressure. Purification of the residue by a silica gel column gave 49.7 g (94% yield) of 1-(2-thienyl)-3,4-dimethyl-cyclopentadiene as a yellow solid. The structure was identified by NMR.

(a2) Synthesis of dimethylbis[2-(2-thienyl)-4,5-dimethylcyclopentadienyl]silane

A 1 l glass reaction vessel was charged with 49.0 g (0.28 mol) of 1-(2-thienyl)-3,4-dimethylcyclopentadiene and 400 ml of THF and the mixture was cooled to −30° C. on a dry ice/methanol bath. To the mixture were added dropwise 183 ml (0.28 mol) of an n-butyllithium/hexane solution of 1.52 mol/l. After the addition was completed, the mixture was raised slowly to room temperature and stirred for 2 hrs. The mixture was again cooled to −30° C. on a dry ice/methanol bath and 100 ml of a THF solution containing 17.9 g (0.14 mol) of dimethyl dichlorosilane were added dropwise. After the addition was completed, the mixture was raised slowly to room temperature and stirred for 16 hrs.

To the reaction solution was added distilled water. The suspended matter was filtered off, and the solution was then transferred into a separatory funnel and washed with brine until it was neutral. Anhydrous sodium sulfate was added and the reaction solution was allowed to stand overnight and dried. Anhydrous sodium sulfate was filtered off and the solvent was distilled off under reduced pressure. Purification of the residue by a silica gel column and recrystallization with toluene/hexane gave 35.1 g (62% yield) of dimethylbis[2-(2-thienyl)-4,5-dimethylcyclopentadienyl]silane as yellow crystals.

(b) Synthesis of dimethylsilylenebis[2-(2-thienyl)-4,5-dimethylcyclopentadienyl]zirconium dichloride

A 500 ml glass reaction vessel was charged with 13.5 g (0.033 mol) of dimethylbis[2-(2-thienyl)-4,5-dimethylcyclopentadienyl]silane and 300 ml of diethyl ether and the mixture was cooled to −70° C. on a dry ice/methanol bath. To the mixture were added dropwise 43 ml (0.065 mol) of an n-butyllithium/hexane solution of 1.52 mol/l. After the addition was completed, the mixture was raised slowly to room temperature and stirred for 16 hrs. The solvent was distilled off under reduced pressure. To the residue was added 400 ml of toluene and the mixture was cooled to −70° C. on a dry ice/methanol bath. 7.7 g (0.033 mol) of zirconium tetrachloride in a solid state was added. Subsequently the mixture was raised slowly to room temperature, stirred for 16 hrs and heated at 80° C. in an oil bath.

Recrystallization with toluene/hexane gave 110 mg of dimethylsilylenebis[2-(2-thienyl)-4,5-dimethylcyclopentadienyl]zirconium dichloride as red crystals (racemic form, purity 99% or more).

1 H-NMR (CDC1 3 ) Racemic form δ: 0.81 (s, 6H), δ: 1.54 (s, 6H), δ: 2.22 (s, 6H), δ: 6.69 (s, 2H), δ: 6.94 (dd, 2H), δ: 7.11 (dd, 2H), δ: 7.27 (dd, 2H).

Polymerization of propylene using dimethylsilylenebis[2-(2-thienyl)-4,5-dimethylcyclopentadienyl]zirconium dichloride

A SUS autoclave was charged successively with 1 liter of toluene, a toluene solution of methylaluminoxane (MMAO3A, manufactured by Toso-Aczo Co., Ltd.) (Al/Zr=10,000) and 3 ml (1.05×10 −6 mol) of a toluene solution of dimethylsilylenebis[2-(2-thienyl)-4,5-dimethylcyclopentadienyl]zirconium dichloride, and the mixture was heated to 30° C. Into the autoclave was introduced propylene at a pressure of 0.3 MPaG and a polymerization was carried out for one hour. After the polymerization was completed, a catalyst component was decomposed with 1 liter of hydrochloric acidic methanol. Subsequently, filtration, washing and drying were carried out to obtain 1.88 g of polypropylene.

The analytical values for the resultant polypropylene are shown in Table 1.

Example 8

Synthesis of dimethylsilylenebis[2-(2-(5-methyl)furyl)-4,5-dimethylcyclopentadienyl]zirconium dichloride

(a1) Synthesis of 1-(2-(5-methyl)furyl)-3,4-dimethylcyclopentadiene

A 1 l glass reaction vessel was charged with 30.0 g (0.37 mol) of 2-methylfuran and 400 ml of THF and the mixture was cooled to −70° C. on a dry ice/methanol bath. To the mixture was added dropwise 236 ml (0.37 mol) of an n-butyllithium/hexane solution of 1.57 mol/l. After the addition was completed, the mixture was raised to room temperature and stirred for 16 hrs. The mixture was again cooled to −30° C. on a dry ice/methanol bath and 100 ml of a THF solution containing 40.8 g (0.37 mol) of 3,4-dimethylcyclopenten-1-one were added dropwise. After the addition was completed, the mixture was raised to room temperature and stirred for 16 hrs.

To the reaction solution was added distilled water. This solution was transferred into a separatory funnel and washed three times with brine. Subsequently, the solution was shaken twice with 50 ml of 0.5N hydrochloric acid and washed with brine until it was neutral. Anhydrous sodium sulfate was added and the solution was allowed to stand overnight and dried. Anhydrous sodium sulfate was filtered off and the solvent was distilled off under reduced pressure. Purification of the residue by a silica gel column gave 47.0 g (90% yield) of 1-(2-(5-metyl)furyl)-3,4-dimethylcyclopentadiene as a red liquid. The structure was identified by NMR.

(a2) Synthesis of dimethylbis[2-(2-(5-methyl)furyl)-4,5-dimethylcyclopentadienyl]silane

A 1 l glass reaction vessel was charged with 47.0 g (0.27 mol) of 1-(2-(5-methyl)furyl)-3,4-dimethylcyclopentadiene, 1.0 g (0.008 mol) of coprous isocyanate and 400 ml of THF and the mixture was cooled to −70° C. on a dry ice/methanol bath. To the mixture were added dropwise 175 ml (0.27 mol) of an n-butyllithium/hexane solution of 1.57 mol/l. After the addition was completed, the mixture was raised to room temperature and stirred for 3 hrs. The mixture was again cooled to −40° C. on a dry ice/methanol bath and 50 ml of a THF solution containing 17.4 g (0.13 mol) of dimethyl dichlorosilane were added dropwise. After the addition was completed, the mixture was raised to room temperature and stirred for 16 hrs.

To the reaction solution was added distilled water. This reaction solution was transferred into a separatory funnel and washed with brine until it was neutral. Anhydrous sodium sulfate was added and the solution was allowed to stand overnight and dried. Anhydrous sodium sulfate was filtered off and the solvent was distilled off under reduced pressure. Purification of the residue by a silica gel column and recrystallization with toluene/hexane gave 37.7 g (75% yield) of dimethylbis-[2-(2-(5-methyl)furyl)-4,5-dimethylcyclopentadienyl]silane as yellow crystals.

(b) Synthesis of dimethylsilylenebis[2-(2-(5-methyl)furyl)-4,5-dimethylcyclopentadienyl]zirconium dichloride

A 500 ml glass reaction vessel was charged with 10.0 g (0.027 mol) of dimethylbis[2-(2-(5-methyl)furyl)-4,5-dimethylcyclopentadienyl]silane and 150 ml of THF and the mixture was cooled to −70° C. on a dry ice/methanol bath. To the mixture were added dropwise 35 ml (0.055 mol) of an n-butyllithium/hexane solution of 1.57 mol/l. After the addition was completed, the mixture was raised to room temperature and stirred for 16 hrs. The solvent was distilled off under reduced pressure. To the residue was added 300 ml of toluene and the mixture was cooled to −70° C. on a dry ice/methanol bath. 6.3 g (0.027 mol) of zirconium tetrachloride in a solid state was added. Subsequently the mixture was raised to room temperature, stirred for 16 hrs and heated at 80° C. for 4 hrs. A part of the reaction solution was withdrawn and determined by 1 H-NMR, by which it was found to be a mixture of a racemic form/meso form (molar ratio=55/45).

The solvent was distilled off under reduced pressure. The residue was extracted with hexane to obtain 7.8 g (51% yield) of dimethylsilylenebis[2-(2-(5-methyl)-furyl)-4,5-dimethylcyclopentadienyl]zirconium dichloride as yellow powders. Further recrystallization gave 520 mg of the racemic form (purity 99% or more) and 230 mg of the meso form (purity 99% or more). 1 H-NMR (CDCl 3 ) Racemic form δ: 0.80 (s, 6H), δ: 1.49 (s, 6H), δ: 2.18 (s, 6H), δ: 2.31 (s, 6H), δ: 6.01 (dd, 2H), d: 6.41 (d, 2H), δ: 6.67 (s, 2H)

Meso form δ: 0.69 (s, 3H), δ: 0.99 (s, 3H), δ: 2.00 (s, 6H), δ: 2.19 (s, 6H), δ: 2.27 (s, 6H), δ: 6.12 (dd, 2H), δ: 5.73 (d, 2H), δ: 6.61 (s, 2H).

Polymerization of propylene using dimethylsilylenebis[2-(2-(5-methyl)furyl)-4,5-dimethylcyclopentadienyl]zirconium dichloride

A SUS autoclave was charged successively with 1 liter of toluene, a toluene solution of methylaluminoxane (MMAO3A, manufactured by Toso-Aczo Co., Ltd.) (Al/Zr=10,000) and 3 ml (1.08×10 −6 mol) of a toluene solution of dimethylsilylenebis[2-(2-(5-methyl)-furyl)-4,5-dimethylcyclopentadienyl]zirconium dichloride, and the mixture was heated to 30° C. Into the autoclave was introduced propylene at a pressure of 0.3 MPaG and a polymerization was carried out for one hour. After the polymerization was completed, a catalyst component was decomposed with 1 liter of hydrochloric acidic methanol. Subsequently, filtration, washing and drying were carried out to obtain 26.8 g of polypropylene.

The analytical values for the resultant polypropylene are shown in Table 1.

Example 9

Synthesis of dimethylsilylenebis[2-(2-(5-t-butyl)furyl)-4,5-dimethylcyclopentadienyl]zirconium dichloride

(a1) Synthesis of 1-(2-(5-t-butyl)furyl)-3,4-dimethylcyclopentadiene

A 1 l glass reaction vessel was charged with 25.0 g (0.20 mol) of 2-t-butylfuran and 300 ml of THF and cooled to −70° C. on a dry ice/methanol bath. To the mixture were added dropwise 135 ml (0.21 mmol) of an n-butyllithium/hexane solution of 1.54 mol/l. After the addition was completed, the mixture was raised to room temperature and stirred for 16 hrs. The mixture was again cooled to −30° C. on a dry ice/methanol bath and 100 ml of a THF solution containing 22.0 g (0.20 mol) of 3,4-dimethylcyclopenten-1-one were added dropwise. After the addition was completed, the mixture was raised to room temperature and stirred for 16 hrs.

To the reaction solution was added distilled water. This solution was transferred into a separatory funnel and washed three times with brine. Subsequently, the solution was shaken twice with 50 ml of 0.5N hydrochloric acid and washed with brine until it was neutral. Anhydrous sodium sulfate was added and the solution was allowed to stand overnight and dried. Anhydrous sodium sulfate was filtered off and the solvent was distilled off under reduced pressure. Purification of the residue by a silica gel column gave 37.9 g (88% yield) of 1-(2-(5-t-butyl)furyl)3,4-dimethylcyclopentadiene as a red liquid. The structure was identified by NMR.

(a2) Synthesis of dimethylbis[2-(2-(5-t-butyl)furyl)-4,5-dimethylcyclopentadienyl]silane

A 1 l glass reaction vessel was charged with 37.9 g (0.18 mol) of 1-(2-(5-t-butyl)furyl)-3,4-dimethylcyclopentadiene, 1.0 g (0.008 mol) of coprous isocyanate and 300 ml of THF and the mixture was cooled to −70° C. on a dry ice/methanol bath. To the mixture were added dropwise 120 ml (0.18 mol) of an n-butyllithium/hexane solution of 1.54 mol/l. After the addition was completed, the mixture was raised to room temperature and stirred for 3 hrs. The mixture was again cooled to −40° C. on a dry ice/methanol bath and 50 ml of a THF solution containing 11.3 g (0.088 mol) of dimethyl dichlorosilane were added dropwise. After the addition was completed, the mixture was raised to room temperature and stirred for 16 hrs.

To the reaction solution was added distilled water. This reaction solution was transferred into a separatory funnel and washed with brine until it was neutral. Anhydrous sodium sulfate was added and the solution was allowed to stand overnight and dried. Anhydrous sodium sulfate was filtered off and the solvent was distilled off under reduced pressure. Purification of the residue by a silica gel column and recrystallization with toluene/hexane gave 31.1 g (72% yield) of dimethylbis-[2-(2-(5-t-butyl)furyl)-4,5-dimethylcyclopentadienyl]silane as colorless crystals.

(b) Synthesis of dimethylsilylenebis[2-(2-(5-t-butyl)-furyl)-4,5-dimethylcyclopentadienyl]zirconium dichloride

A 500 ml glass reaction vessel was charged with 12.0 g (0.025 mol) of dimethylbis[2-(2-(5-t-butyl)furyl)-4,5-dimethylcyclopentadienyl]silane and 150 ml of THF and the mixture was cooled to −70° C. on a dry ice/methanol bath. To the mixture were added dropwise 33 ml (0.051 mol) of an n-butyllithium/hexane solution of 1.54 mol/l. After the addition was completed, the mixture was raised to room temperature and stirred for 16 hrs. The solvent was distilled off under reduced pressure. To the residue was added 300 ml of toluene and the mixture was cooled to −70° C. on a dry ice/methanol bath. 5.8 g (0.025 mol) of zirconium tetrachloride in a solid state were added. Subsequently the mixture was raised to room temperature and stirred for 3 days. A part of the reaction solution was withdrawn and determined by 1 H-NMR, by which it was found to be a mixture of a racemic form/meso form (molar ratio=50/50).

The solvent was distilled off under reduced pressure. The residue was extracted with hexane to obtain 12.9 g (81% yield) of dimethylsilylenebis[2-(2-(5-t-butyl)furyl)-4,5-dimethylcyclopentadienyl]zirconium dichloride as yellow powders. Further recrystallization gave 770 mg of the racemic form (purity 99% or more) and 170 mg of the meso form (purity 99% or more). 1 H-NMR (CDCl 3 ) Racemic form δ: 0.78 (s, 6H), δ: 1.29 (s, 18H), δ: 1.55 (s, 6H), δ: 2.20 (s, 6H), δ: 5.92 (d, 2H), δ: 6.42 (d, 2H), δ: 6.68 (s, 2H)

Meso form δ: 0.57 (s, 3H), δ: 0.99 (s, 3H), δ: 1.24 (s, 18H), δ: 2.01 (s, 6H), δ: 2.28 (s, 6H), δ: 5.68 (d, 2H), δ: 5.99 (d, 2H), δ: 6.63 (s, 2H).

Polymerization of propylene using dimethylsilylenebis[2-(2-(5-t-butyl)furyl)-4,5-dimethylcyclopentadienyl]zirconium dichloride

A SUS autoclave was charged successively with 1 liter of toluene, a toluene solution of methylaluminoxane (MMAO3A, manufactured by Toso-Aczo Co., Ltd.) (Al/Zr=10,000) and 3 ml of a toluene solution of dimethylsilylene-bis[2-(2-(5-t-butyl)furyl)-4,5-dimethylcyclopentadienyl]-zirconium dichloride (1.02×10 −6 mol), and the mixture was heated to 30° C. Into the autoclave was introduced propylene at a pressure of 0.3 MPaG and a polymerization was carried out for one hour. After the polymerization was completed, a catalyst component was decomposed with 1 liter of hydrochloric acidic methanol. Subsequently, filtration, washing and drying were carried out to obtain 33.1 g of polypropylene.

The analytical values for the resultant polypropylene are shown in Table 1.

Example 10

Synthesis of dimethylsilylenebis[2-(2-(5-trimethylsilyl)-furyl)-4,5-dimethylcyclopentadienyl]zirconium dichloride

(a1) Synthesis of 1-(2-(5-trimethylsilyl)furyl)-3,4-dimethylcyclopentadiene

A 1 l glass reaction vessel was charged with 23.0 g (0.16 mol) of 2-trimethylsilylfuran and 200 ml of THF and the mixture was cooled to −70° C. on a dry ice/methanol bath. To the mixture were added dropwise 100 ml (0.16 mmol) of an n-butyllithium/hexane solution of 1.57 mol/l. After the addition was completed, the mixture was raised to room temperature and stirred for 16 hrs. The mixture was again cooled to −30° C. on a dry ice/methanol bath and 100 ml of a THF solution containing 17.3 g (0.16 mol) of 3,4-dimethylcyclopenten-1-one were added dropwise. After the addition was completed, the mixture was raised to room temperature and stirred for 16 hrs.

To the reaction solution was added distilled water. This reaction solution was transferred into a separatory funnel and washed three times with brine. This solution was then shaken twice with 50 ml of 0.5N hydrochloric acid and washed with brine until it was neutral. Anhydrous sodium sulfate was added and the solution was allowed to stand overnight and dried. Anhydrous sodium sulfate was filtered off and the solvent was distilled off under reduced pressure. Purification of the residue by a silica gel column gave 31.5 g (85% yield) of 1-(2-(5-trimethylsilyl)furyl)-3,4-dimethylcyclopentadiene as a yellow liquid. The structure was identified by NMR.

(a2) Synthesis of dimethylbis[2-(2-(5-trimethylsilyl)furyl)4,5-dimethylcyclopentadienyl]silane

A 1 l glass reaction vessel was charged with 31.5 g (0.14 mol) of 1-(2-(5-trimethylsilyl)furyl)-3,4-dimethylcyclopentadiene, 1.0 g (0.008 mol) of coprous isocyanate and 300 ml of THF and the mixture was cooled to −70° C. on a dry ice/methanol bath. To the mixture was added dropwise 90 ml (0.14 mmol) of an n-butyllithium/hexane solution of 1.57 mol/l. After the addition was completed, the mixture was raised to room temperature and stirred for 16 hrs. The mixture was again cooled to −30° C. on a dry ice/methanol bath and 50 ml of a THF solution containing 8.7 g (0.067 mol) of dimethyl dichlorosilane were added dropwise. After the addition was completed, the mixture was raised to room temperature and stirred for 16 hrs.

To the reaction solution was added distilled water. This reaction solution was transferred into a separatory funnel and washed with brine until it was neutral. Anhydrous sodium sulfate was added and the solution was allowed to stand overnight and dried. Anhydrous sodium sulfate was filtered off and the solvent was distilled off under reduced pressure. Purification of the residue by a silica gel column and recrystallization with toluene/hexane gave 24.7 g (70% yield) of dimethylbis[2-(2-(5-trimethylsilyl)furyl)-4,5-dimethylcyclopentadienyl]silane as pale yellow crystals. Synthesis of dimethylsilylenebis[2-(2-(5-trimethylsilyl)furyl)-4,5-dimethylcyclopentadienyl]zirconium dichloride

A 500 ml glass reaction vessel was charged with 12.0 g (0.023 mol) of dimethylbis[2-(2-(5-trimethylsilyl)furyl)-4,5-dimethyl-cyclopentadienyl]silane and 150 ml of THF and cooled to −70° C. on a dry ice/methanol bath. To the mixture was added dropwise 31 ml (0.049 mmol) of an n-butyllithium/hexane solution of 1.57 mol/l. After the addition was completed, the mixture was raised to room temperature and stirred for 16 hrs. The solvent was distilled off. To the residue were added 300 ml of toluene and the mixture was cooled to −70° C. on a dry ice/methanol bath. 5.4 g (0.023 mol) of zirconium tetrachloride in a solid state was added. After the addition was completed, the mixture was raised to room temperature and stirred for 3 days. A part of the reaction solution was withdrawn and determined by 1 H-NMR, by which it was found to be a mixture of a racemic form/meso form (molar ratio=75/25).

The solvent was distilled off under reduced pressure and the residue was extracted with hexane to afford 12.0 g (76% yield) of dimethylsilylenebis[2-(2-(5-trymethylsilyl)furyl)-4,5-dimethylcyclopentadienyl]zirconium dichloride as yellow powders. Further recrystallization gave 2.0 g of the racemic form (purity 99% or more).

1 H-NMR (CDCl 3 ) Racemic form δ: 0.28 (s, 18H), d: 0.79 (s, 6H), δ: 1.45 (s, 6H), δ: 2.18 (s, 6H), δ: 6.56 (d, 2H), δ: 6.61 (d, 2H), δ: 6.71 (s, 2H)

Meso form δ: 0.23 (s, 18H), δ: 0.47 (s, 3H), δ: 1.00 (s, 3H), δ: 2.02 (s, 6H), δ: 2.28 (s, 6H), δ: 6.10 (d, 2H), δ: 6.30 (d, 2H),o: 6.64 (s, 2H).

Polymerization of propylene using dimethylsilylenebis[2-(2-(5-trimethylsilyl)furyl)-4,5-dimethylcyclopentadienyl]zirconium dichloride

A SUS autoclave was charged successively with 1 liter of toluene, a toluene solution of methylaluminoxane (MMAO3A, manufactured by Toso-Aczo Co., Ltd.) (Al/Zr=10,000) and 3 ml (0.97×10 −6 mol) of a toluene solution of dimethylsilylene-bis[2-(2-(5-trimethylsilyl)furyl)-4,5-dimethylcyclopentadienyl]-zirconium dichloride, and the mixture was heated to 30° C. Into the autoclave was introduced propylene at a pressure of 0.3 MPaG and a polymerization was carried out for one hour. After the polymerization was completed, a catalyst component was decomposed with 1 liter of hydrochloric acidic methanol. Subsequently, filtration, washing and drying were carried out to obtain 39.3 g of polypropylene.

The analytical values for the resultant polypropylene are shown in Table 1.

Example 11

Synthesis of dimethylsilylenebis[2-(2-(4,5-dimethyl)furyl)4,5-dimethylcyclopentadienyl]zirconium dichloride

(a1) Synthesis of 1-(2-(4,5-dimethyl)furyl)-3,4-dimethylcyclopentadiene

A 1 l glass reaction vessel was charged with 17.0 g (0.18 mol) of 2,3-dimethylfuran and 300 ml of THF and cooled to −70° C. on a dry ice/methanol bath. To the mixture were added dropwise 115 ml (0.18 mol) of an n-butyllithium/hexane solution of 1.54 mol/l. After the addition was completed, the mixture was raised to room temperature and stirred for 16 hrs. The mixture was again cooled to −30° C. on a dry ice/methanol bath and 100 ml of a THF solution containing 19.5 g (0.18 mol) of 3,4-dimethylcyclopenten-1-one were added dropwise. After the addition was completed, the mixture was raised to room temperature and stirred for 16 hrs.

To the reaction solution was added distilled water. This reaction solution was transferred into a separatory funnel and washed three times with brine. This solution was then shaken twice with 50 ml of 0.5N hydrochloric acid and washed with brine until it was neutral. Anhydrous sodium sulfate was added and the solution was allowed to stand overnight and dried. Anhydrous sodium sulfate was filtered off and the solvent was distilled off under reduced pressure. Purification of the residue by a silica gel column gave 30.6 g (92% yield) of 1-(2-(4,5-dimethyl)furyl)-3,4-dimethylcyclopentadiene as orange crystals. The structure was identified by NMR.

(a2) Synthesis of dimethylbis[2-(2-(4,5-dimethyl)furyl)-4,5-dimethylcyclopentadienyl]silane

A 1 l glass reaction vessel was charged with 30.0 g (0.16 mol) of 1-(2-(4,5-dimethyl)furyl)-3,4-dimethylcyclopentadiene, 1.0 g (0.008 mol) of coprous isocyanate and 300 ml of THF and the mixture was cooled to −70° C. on a dry ice/methanol bath. To the mixture were added dropwise 108 ml (0.16 mol) of an n-butyllithium/hexane solution of 1.57 mol/l. After the addition was completed, the mixture was raised to room temperature and stirred for 16 hrs. The mixture was again cooled to −30° C. on a dry ice/methanol bath and 50 ml of a THF solution containing 10.3 g (0.080 mol) of dimethyl-dichlorosilane were added dropwise. After the addition was completed, the mixture was raised to room temperature and stirred for 16 hrs.

To the reaction solution was added distilled water. This reaction solution was transferred into a separatory funnel and washed with brine until it was neutral. Anhydrous sodium sulfate was added and the solution was allowed to stand overnight and dried. Anhydrous sodium sulfate was filtered off and the solvent was distilled off under reduced pressure. Purification of the residue by a silica gel column and recrystallization with toluene/hexane gave 21.3 g (62% yield) of dimethylbis[2-(2-(4,5-dimethyl)furyl)-4,5-dimethylcyclopentadienyl]silane as pale yellow crystals.

(b) Synthesis of dimethylsilylenebis[2-(2-(4,5-dimethyl)furyl)-4,5-dimethylcyclopentadienyl]zirconium dichloride

A 500 ml glass reaction vessel was charged with 12.0 g (0.025 mol) of dimethylbis[2-(2-(4,5-dimethyl)furyl)4,5-dimethylcyclopentadienyl]silane and 150 ml of THF and the mixture was cooled to −70° C. on a dry ice/methanol bath. To the mixture were added dropwise 33 ml (0.051 mmol) of an n-butyllithium/ hexane solution of 1.54 mol/l. After the addition was completed, the mixture was raised to room temperature and stirred for 16 hrs. The solvent was distilled off. To the residue were added 300 ml of toluene is and the mixture was cooled to −70° C. on a dry ice/methanol bath. 5.8 g (0.025 mol) of zirconium tetrachloride in a solid state was added. Subsequently, the mixture was raised to room temperature and stirred for 3 days. A part of the reaction solution was withdrawn and determined by 1 H-NMR, by which it was found to be a mixture of a racemic form/meso form (molar ratio=62/38).

The solvent was distilled off under reduced pressure and the residue was extracted with hexane to afford 12.9 g (62% yield) of dimethylsilylenebis[2-(2-(4,5-dimethyl)furyl)-4,5-dimethylcyclopentadienyl]zirconium dichloride as yellow powders. Further recrystallization gave 770 mg of the racemic form (purity 99% or more) and 170 mg of the meso form (purity 99% or more).

1 H-NMR (CDCl 3 ) Racemic form δ: 0.80 (s, 6H), δ: 1.49 (s, 6H), δ: 1.92 (s, 6H), δ: 1.99 (s, 6H), δ: 2.18 (s, 6H), δ: 6.30 (s, 2H), δ: 6.64 (s, 2H)

Meso form δ: 0.72 (s, 3H), δ: 0.98 (s, 3H), d: 1.81 (s, 6H), δ: 2.10 (s, 6H), δ: 2.22 (s, 6H), δ: 2.26 (s, 6H), δ: 5.88 (s, 2H),δ: 6.58 (s, 2H).

Polymerization of propylene using dimethylsilylenebis[2-(2-(4,5-dimethyl)furyl)-4,5-dimethylcyclopentadienyl]zirconium dichloride

A SUS autoclave was charged successively with 1 liter of toluene, a toluene solution of methylaluminoxane (MMAO3A, manufactured by Toso-Aczo Co., Ltd.) (Al/Zr=10,000) and 3 ml (1.05×10 −6 mol) of a toluene solution of dimethylsilylenebis[2-(2-(4,5-dimethyl)furyl)-4,5-dimethylcyclopentadienyl]zirconium dichloride, and the mixture was heated to 30° C. Into the autoclave was introduced propylene 20 at a pressure of 0.3 MPaG and a polymerization was carried out for one hour. After the polymerization was completed, a catalyst component was decomposed with 1 liter of hydrochloric acidic methanol. Subsequently, filtration, washing and drying were carried out to obtain 13.3 g of polypropylene.

The analytical values for the resultant polypropylene are shown in Table 1.

Example 12

Synthesis of dimethylsilylenebis[2-(2-benzofuryl)-4,5-dimethylcyclopentadienyl]zirconium dichloride

(a1) Synthesis of 1-(2-benzofuryl)-3,4-dimethylcyclopentadiene

A 1 l glass reaction vessel was charged with 34.4 g (0.29 mol) of benzofuran and 400 ml of THF and the mixture was cooled to −70° C. on a dry ice/methanol bath. To the mixture were added dropwise 180 ml (0.28 mol) of an n-butyllithium/hexane solution of 1.53 mol/l. After the addition was completed, the mixture was raised to room temperature and stirred for 16 hrs. The mixture was again cooled to −30° C. on a dry ice/methanol bath and 100 ml of a THF solution containing 30.0 g (0.27 mol) of 3,4-dimethylcyclopenten-1-one were added dropwise. After the addition was completed, the mixture was raised to room temperature and stirred for 16 hrs.

To the reaction solution was added distilled water. This reaction solution was transferred into a separatory funnel and washed three times with brine. This solution was then shaken twice with 30 ml of 2N hydrochloric acid and washed with brine until it was neutral. Anhydrous sodium sulfate was added and the reaction solution was allowed to stand overnight and dried. Anhydrous sodium sulfate was filtered off and the solvent was distilled off under reduced pressure. Purification of the residue by a silica gel column gave 54.3 g (95% yield) of 1-(2-benzofuryl)-3,4-dimethylcyclopentadiene as pale yellow crystals. The structure was identified by NMR.

(a2) Synthesis of dimethylbis[2-(2-benzofuryl)-4,5-dimethylcyclopentadienyl]silane

A 1 l glass reaction vessel was charged with 54.3 g (0.26 mol) of 1-(2-benzofuryl)-3,4-dimethylcyclopentadiene, 1.5 g (0.012 mol) of coprous isocyanate and 400 ml of THF and the mixture was cooled to −70° C. on a dry ice/methanol bath. To the mixture were added dropwise 170 ml (0.26 mol) of an n-butyllithium/hexane solution of 1.53 mol/l. After the addition was completed, the mixture was raised to room temperature and stirred for 16 hrs. The mixture was again cooled to −70° C. on a dry ice/methanol bath and 100 ml of a THF solution containing 16.6 g (0.13 mol) of dimethyl dichlorosilane were added dropwise. After the addition was completed, the mixture was raised to room temperature and stirred for 16 hrs.

To the reaction solution was added distilled water. This reaction solution was transferred into a separatory funnel and washed with brine until it was neutral. Anhydrous sodium sulfate was added and the solution was allowed to stand overnight and dried. Anhydrous sodium sulfate was filtered off and the solvent was distilled off under reduced pressure. Purification of the residue by a silica gel column and recrystallization with toluene/hexane gave 19 g (46% yield) of dimethylbis[2-(2-benzofuryl)-4,5-dimethylcyclopentadienyl]silane as pale yellow crystals.

(b) Synthesis of dimethylsilylenebis[2-(2-benzofuryl)-4,5-dimethylcyclopentadienyl]zirconium dichloride

A 500 ml glass reaction vessel was charged with 15.0 g (0.031 mol) of dimethylbis[2-(2-benzofuryl)-4,5-dimethylcyclopentadienyl]silane and 300 ml of THF and the mixture was cooled to −70° C. on a dry ice/methanol bath. To the mixture were added dropwise 41 ml (0.063 mol) of an n-butyllithium/hexane solution of 1.53 mol/l. After the addition was completed, the mixture was raised to room temperature and stirred for 16 hrs. The solvent was distilled off. To the residue were added 400 ml of toluene and the mixture was cooled to −70° C. on a dry ice/methanol bath. 7.2 g (0.031 mol) of zirconium tetrachloride in a solid state was added. Subsequently, the mixture was raised to room temperature and stirred for 3 days. A part of the reaction solution was withdrawn and determined by 1 H-NMR, by which it was found to be a mixture of a racemic form/meso form (molar ratio=40/60).

The solvent was distilled off under reduced pressure and the residue was extracted with hexane to afford 6.0 g (30% yield) of dimethylsilylenebis[2-(2-benzofuryl)-4,5-dimethylcyclopentadienyl]zirconium dichloride as yellow powders. Further recrystallization gave 510 mg of the racemic form (purity 99% or more).

1 H-NMR (CDC1 3 ) Racemic form δ: 0.92 (s, 6H), δ: 1.46 (s, 6H), δ: 2.22 (s, 6H), δ: 6.89 (s, 2H), δ: 6.97 (s, 2H), δ: 7.22-7.31 (m, 4H), δ: 6.96 (d, 2H), δ: 7.57 (d, 2H)

Meso form δ: 0.94 (s, 3H), δ: 1.08 (s, 3H), δ: 2.08 (s, 6H), δ: 2.34 (s, 6H), δ: 6.37 (s, 2H), δ: 6.82 (s, 2H), δ: 6.79-6.86 (m, 4H), δ: 6.93-6.96 (m, 2H), δ: 7.03 (d, 2H).

Polymerization of propylene using dimethylsilylenebis[2-(2-benzofuryl)-4,5-dimethylcyclopentadienyl]zirconium dichloride

A SUS autoclave was charged successively with 1 liter of toluene, a toluene solution of methylaluminoxane (MMAO3A, manufactured by Toso-Aczo Co., Ltd.) (Al/Zr=10,000) and 3 ml (1.55×10 −6 mol) of a toluene solution of dimethylsilylenebis(2-(2-benzofuryl)-4,5-dimethylcyclopentadienyl]zirconium dichloride, and the mixture was heated to 30° C. Into the autoclave was introduced propylene at a pressure of 0.3 MPaG and a polymerization was carried out for one hour. After the polymerization was completed, a catalyst component was decomposed with 1 liter of hydrochloric acidic methanol. Subsequently, filtration, washing and drying were carried out to obtain 14.3 g of polypropylene.

The analytical values for the resultant polypropylene are shown in Table 1.

Example 12

Synthesis of dimethylsilylenebis[2-(2-thienyl)-indenyl]zirconium dichloride

(a1) Synthesis of 2-(2-thienyl)-indene

A 500 ml glass reaction vessel was charged with 12.8 g (0.15 mol) of thiophene and 200 ml of THF and the mixture was cooled to −70° C. on a dry ice/methanol bath. To the mixture were added dropwise 100 ml (0.15 mol) of an n-butyllithium/hexane solution of 1.53 mol/l. After the addition was completed, the mixture was raised to room temperature and stirred for 3 hrs. The mixture was again cooled to −20° C. on a dry ice/methanol bath and 200 ml of a THF solution containing 20.0 g (0.15 mol) of 2-indanone were added dropwise. After the addition was completed, the mixture was raised to room temperature and stirred for 16 hrs.

To the reaction solution was added distilled water. This reaction solution was transferred into a separatory funnel and washed with brine until it was neutral. Anhydrous sodium sulfate was added and the reaction solution was allowed to stand overnight and dried. Anhydrous sodium sulfate was filtered off and the solvent was distilled off under reduced pressure. To the residue were added 200 ml of toluene and 0.5 g of P-toluenesulfonic acid. The mixture was heated under reflux while removing water that was distilling out. The reaction solution was transferred into a separatory funnel and washed with brine until it was neutral. Anhydrous sodium sulfate was added and the solution was allowed to stand overnight and dried. Anhydrous sodium sulfate was filtered off and the solvent was distilled off under reduced pressure. Purification of the residue by a silica gel column gave 3.2 g (25% yield) of 2-(2-thienyl)-indene as pale yellow-green crystals. The structure was identified by NMR.

(a2) Synthesis of dimethylbis[2-(2-thienyl)-indenyl]silane

A 200 ml glass reaction vessel was charged with 10.0 g (0.051 mol) of 2-(2-thienyl)-indene, 0.87 g (0.0072 mol) of coprous cyanide and 210 ml of THF and the mixture was cooled to −70° C. on a dry ice/methanol bath. To the mixture were added dropwise 36 ml (0.057 mol) of an n-butyllithium/hexane solution of 1.57 mol/l. After the addition was completed, the mixture was raised to room temperature and stirred for 16 hrs. The mixture was again cooled to −70° C. on a dry ice/methanol bath and 140 ml of a THF solution containing 3.7 g (0.028 mol) of dimethyl dichlorosilane were added dropwise. After the addition was completed, the mixture was raised to room temperature and stirred for 16 hrs.

To the reaction solution was added distilled water. This reaction solution was transferred into a separatory funnel and washed with brine until it was neutral. Anhydrous sodium sulfate was added and the reaction solution was allowed to stand overnight and dried. Anhydrous sodium sulfate was filtered off and the solvent was distilled off under reduced pressure. Purification of the residue by a silica gel column gave 7.3 g (64% yield) of dimethylbis[2-(2-thienyl)-indenyl]silane as pale yellow-green crystals.

(b) Synthesis of dimethylsilylenebis[2-(2-thienyl)-indenyl]zirconium dichloride

A 100 ml glass reaction vessel was charged with 12.4 g (0.027 mol) of dimethylbis[2-(2-thienyl)-indenyl]-silane and 30 ml of THF and the mixture was cooled to −70° C. on a dry ice/methanol bath. To the mixture were added dropwise 35 ml (0.055 mol) of an n-butyllithium/hexane solution of 1.57 mol/l. After the addition was completed, the mixture was raised to room temperature and stirred for 16 hrs. The solvent was distilled off. To the residue were added 400 ml of toluene and the mixture was cooled to −70° C. on a dry ice/methanol bath. 6.3 g (0.027 mol) of zirconium tetrachloride were added. Subsequently, the mixture was raised to room temperature and stirred for 16 hrs. A part of the reaction solution was withdrawn and determined by 1 H-NMR, by which it was found to be a mixture of a racemic form/meso form (molar ratio=75/25).

The solvent was distilled off under reduced pressure and the residue was extracted with toluene to afford 100 mg (0.6% yield) of the racemic form (purity 99% or more).

1 H-NMR (CDCl 3 ) Racemic form δ: 1.03 (s, 6H), δ: 7.04 (s, 2H), δ: 6.80-7.63 (m, 14H). Polymerization of propylene using dimethylsilylenebis[2-(2-thienyl)-indenyl] zirconium dichiloride

A SUS autoclave was charged successively with 1 liter of toluene, a toluene solution of methylaluminoxane (MMAO3A, manufactured by Toso-Aczo Co., Ltd.) (Al/Zr=10,000) and 3 ml (2.71×10 −6 mol) of a toluene solution of dimethylsilylenebis[2-(2-thienyl)-indenyl]zirconium dichloride, and the mixture was heated to 30° C. Into the autoclave was introduced propylene at a pressure of 0.3 MPaG and a polymerization was carried out for one hour. After the polymerization was completed, a catalyst component was decomposed with 1 liter of hydrochloric acidic methanol. Subsequently, filtration, washing and drying were carried out to obtain 1.88 g of polypropylene.

The analytical values for the resultant polypropylene are shown in Table 1.

In Table 1, “Amount of racemic form” indicates the amount of a racemic form in the metallocene complex used as the catalyst in the polymerization of propylene. In case of a mixture of a racemic/meso form being used as the catalyst, the amount of the mixture used was indicated in parenthesis. The amount of a racemic form in the mixture was calculated from a molar ratio of a racemic/meso form determined by NMR for the mixture, and the calculated value was indicated in the table. In case of propylene being polymerized using a mixture of a racemic/meso form as the catalyst, the amount of an isotactic polypropylene component obtained by removing an atactic polypropylene component from the polymerization product was indicated as “yield” in the table. “Activity” was calculated from the values shown in “amount of racemic form” and “yield”.

TABLE 1
Analytical Values for Polypropylene
	Amount of
	racemic		Activity
Metallocene	form		kg-pp/
compound of	× 10 −6	Yield	mmol-	Mw		Tm
Example No.	mol	g	M-h	× 10 4	Mw/Mn	° C.	Mmmm
1	0.65	43.1	67	13.3	1.77	153.6	0.941
Me 2 Si[3-(2-	(1.35)
Furyl)-2,5-
Me 2 —Cp] 2 ZrCl 2
2	0.62	42.7	69	48.3	1.91	156.9	0.956
Me 2 Si[2-(2-
Furyl)-3,5-
Me 2 —Cp] 2 ZrCl 2
3	0.55	20.9	38	47.8	2.01	154.0	0.943
Me 2 Si[2-(2-
Furyl)-4,5-
Me 2 —Cp] 2 ZrCl 2
4	0.97	33.6	35	23.8	1.77	148.9	0.938
Me 2 Si[3-(2-	(1.61)
Thienyl)-2,5-
Me 2 —Cp] 2 ZrCl 2
5	0.30	4.6	15	128	2.30	148.0	0.925
Me 2 Si[2-(2-
Furyl)-
Indenyl]ZrCl 2
7	1.05	1.88	1.8	9.75	1.83	77.1	0.460
Me 2 Si(2-2-
Thienyl)-4,5-
Me 2 —Cp) 2 ZrCl 2
8	1.08	26.8	25	63.5	2.02	154.8	0.954
Me 2 Si(2-(2-
(5-Me)-
Furyl)-4,5-
Me 2 —Cp) 2 ZrCl 2
9	1.02	33.1	32	58.5	2.20	152.0	0.940
Me 2 Si(2-(2-
(5-t-Bu)-
Furyl)-4,5-
Me 2 —Cp) 2 ZrCl 2
10	0.97	39.3	40	63.3	1.91	151.5	0.941
Me 2 Si(2-(2-
(5-TMS)-
Furyl)-4,5-
Me 2 —Cp) 2 ZrCl 2
11	1.05	13.3	13	55.8	2.06	155.9	0.959
Me 2 Si(2-(2-
(4,5-Me 2 )-
Furyl)-4,5-
Me 2 —Cp) 2 ZrCl 2
12	1.55	14.3	9.2	37.6	1.83	151.7	0.935
Me 2 Si(2-(2-
BenzoFuryl)-
4,5-Me 2 —
Cp) 2 ZrCl 2
13	2.71	10.7	4.0	42.1	1.91	136.7	0.866
Me 2 Si(2-(2-
Thienyl)-
Ind) 2 ZrCl 2

	TABLE 2
	CA 1 : Cyclopentadienyl	CA 2 : Cyclopentadienyl
No.	M	X	Ra	R 1	p + m	Ra	R 1	q + n	Y
1	Zr	Cl	2-(2-Fu)	—	1	2-(2-Fu)	—	1	—CH 2 —
2	Zr	Cl	2-(2-Fu)	—	1	2-(2-Fu)	—	1	—C(Me) 2 —
3	Zr	Cl	2-(2-Fu)	5-Me	2	2-(2-Fu)	5-Me	2	—C(Me) 2 —
4	Zr	Cl	2-(2-Fu)	4-Me	2	2-(2-Fu)	4-Me	2	—C(Me) 2 —
5	Zr	Cl	2-(2-Fu)	4-OMe	2	2-(2-Fu)	4-OMe	2	—C(Me) 2 —
6	Zr	Cl	2-(2-Fu)	4-OPh	2	2-(2-Fu)	4-OPh	2	—C(Me) 2 —
7	Zr	Cl	2-(2-Fu)	4-Bzl	2	2-(2-Fu)	4-Bzl	2	—C(Me) 2 —
8	Zr	Cl	2-(2-Fu)	4-Tol	2	2-(2-Fu)	4-Tol	2	—C(Me) 2 —
9	Zr	Cl	2-(2-Fu)	4-OBzl	2	2-(2-Fu)	4-OBzl	2	—C(Me) 2 —
10	Zr	Cl	2-(2-Fu)	4-TMS	2	2-(2-Fu)	4-TMS	2	—C(Me) 2 —
11	Zr	Cl	2-(2-Fu)	4-(1-Pyr)	2	2-(2-Fu)	4-(1-Pyr)	2	—C(Me) 2 —
12	Zr	Cl	2-(2-Fu)	4-(1-Indo)	2	2-(2-Fu)	4-(1-Indo)	2	—C(Me) 2 —
13	Zr	Cl	2-(2-Fu)	3-Me	2	2-(2-Fu)	3-Me	2	—C(Me) 2 —
14	Zr	Cl	2-(2-Fu)	3-Me, 5-Me	3	2-(2-Fu)	3-Me, 5-Me	3	—C(Me) 2 —
15	Zr	Cl	2-(2-Fu)	4-Me, 5-Me	3	2-(2-Fu)	4-Me, 5-Me	3	—C(Me) 2 —
16	Zr	Cl	2-(2-Fu)	4-Et, 5-Me	3	2-(2-Fu)	4-Et, 5-Me	3	—C(Me) 2 —
17	Zr	Cl	2-(2-Fu)	4-(i-Pr), 5-Me	3	2-(2-Fu)	4-(i-Pr), 5-Me	3	—C(Me) 2 —
18	Zr	Cl	2-(2-Fu)	4-(t-Bu), 5-Me	3	2-(2-Fu)	4-(t-Bu), 5-Me	3	—C(Me) 2 —
19	Zr	Cl	2-(2-Fu)	4-Ph, 5-Me	3	2-(2-Fu)	4-Ph, 5-Me	3	—C(Me) 2 —
20	Zr	Cl	2-(2-Fu)	3-Ph, 5-Me	3	2-(2-Fu)	3-Ph, 5-Me	3	—C(Me) 2 —
21	Zr	Cl	2-(2-Fu)	4-Me, 5-Me	3	2-(2-Fu)	4-Me, 5-Me	3	—C(Et) 2 —
22	Zr	Cl	2-(2-Fu)	4-Me, 5-Me	3	2-(2-Fu)	4-Me, 5-Me	3	—C(Ph) 2 —
23	Zr	Me	2-(2-Fu)	4-Me, 5-Me	3	2-(2-Fu)	4-Me, 5-Me	3	—C(Me) 2 —
24	Zr	Bzl	2-(2-Fu)	4-Me, 5-Me	3	2-(2-Fu)	4-Me, 5-Me	3	—C(Me) 2 —
25	Hf	Cl	2-(2-Fu)	4-Me, 5-Me	3	2-(2-Fu)	4-Me, 5-Me	3	—C(Me) 2 —
26	Ti	Cl	2-(2-Fu)	4-Me, 5-Me	3	2-(2-Fu)	4-Me, 5-Me	3	—C(Me) 2 —
27	Hf	Cl	2-(2-Fu)	3-Me, 5-Me	3	2-(2-Fu)	3-Me, 5-Me	3	—C(Me) 2 —
28	Ti	Cl	2-(2-Fu)	3-Me, 5-Me	3	2-(2-Fu)	3-Me, 5-Me	3	—C(Me) 2 —
29	Zr	Cl	2-(3-Fu)	4-Me, 5-Me	3	2-(3-Fu)	4-Me, 5-Me	3	—C(Me) 2 —
30	Zr	Cl	2-(3-Fu)	3-Me, 5-Me	3	2-(3-Fu)	3-Me, 5-Me	3	—C(Me) 2 —
31	Zr	Cl	2-[2-(3-Me—Fu)]	4-Me, 5-Me	3	2-[2-(3-Me—Fu)]	4-Me, 5-Me	3	—C(Me) 2 —
32	Zr	Cl	2-[2-(3-Me—Fu)]	3-Me, 5-Me	3	2-[2-(3-Me—Fu)]	3-Me, 5-Me	3	—C(Me) 2 —
33	Zr	Cl	2-(2-Thie)	4-Me, 5-Me	3	2-(2-Thie)	4-Me, 5-Me	3	—C(Me) 2 —
34	Zr	Cl	2-(2-Thie)	3-Me, 5-Me	3	2-(2-Thie)	3-Me, 5-Me	3	—C(Me) 2 —
35	Zr	Cl	2-(2-Py)	4-Me, 5-Me	3	2-(2-Py)	4-Me, 5-Me	3	—C(Me) 2 —
36	Zr	Cl	2-(2-Py)	3-Me, 5-Me	3	2-(2-Py)	3-Me, 5-Me	3	—C(Me) 2 —
37	Zr	Cl	2-(2-BzFu)	4-Me, 5-Me	3	2-(2-BzFu)	4-Me, 5-Me	3	—C(Me) 2 —
38	Zr	Cl	2-(2-BzFu)	3-Me, 5-Me	3	2-(2-BzFu)	3-Me, 5-Me	3	—C(Me) 2 —
39	Zr	Cl	2-[2-(1-Me—Pyr)]	4-Me, 5-Me	3	2-[2-(1-Me—Pyr)]	4-Me, 5-Me	3	—C(Me) 2 —
40	Zr	Cl	2-[2-(1-Me—Pyr)]	3-Me, 5-Me	3	2-[2-(1-Me—Pyr)]	3-Me, 5-Me	3	—C(Me) 2 —

	TABLE 3
	CA 1 : Cyclopentadienyl	CA 2 : Cyclopentadienyl
No.	M	X	Ra	R 1	p + m	Ra	R 1	q + n	Y
41	Zr	Cl	2-(2-Fu)	—	1	2-(2-Fu)	—	1	—CH 2 CH 2 —
42	Zr	Cl	2-(2-Fu)	—	1	2-(2-Fu)	—	1	—C 2 (Me) 4 —
43	Zr	Cl	2-(2-Fu)	5-Me	2	2-(2-Fu)	5-Me	2	—C 2 (Me) 4 —
44	Zr	Cl	2-(2-Fu)	4-Me	2	2-(2-Fu)	4-Me	2	—C 2 (Me) 4 —
45	Zr	Cl	2-(2-Fu)	4-OMe	2	2-(2-Fu)	4-OMe	2	—C 2 (Me) 4 —
46	Zr	Cl	2-(2-Fu)	4-OPh	2	2-(2-Fu)	4-OPh	2	—C 2 (Me) 4 —
47	Zr	Cl	2-(2-Fu)	4-Bzl	2	2-(2-Fu)	4-Bzl	2	—C 2 (Me) 4 —
48	Zr	Cl	2-(2-Fu)	4-Tol	2	2-(2-Fu)	4-Tol	2	—C 2 (Me) 4 —
49	Zr	Cl	2-(2-Fu)	4-OBzl	2	2-(2-Fu)	4-OBzl	2	—C 2 (Me) 4 —
50	Zr	Cl	2-(2-Fu)	4-TMS	2	2-(2-Fu)	4-TMS	2	—C 2 (Me) 4 —
51	Zr	Cl	2-(2-Fu)	4-(1-Pyr)	2	2-(2-Fu)	4-(1-Pyr)	2	—C 2 (Me) 4 —
52	Zr	Cl	2-(2-Fu)	4-(1-Indo)	2	2-(2-Fu)	4-(1-Indo)	2	—C 2 (Me) 4 —
53	Zr	Cl	2-(2-Fu)	3-Me	2	2-(2-Fu)	3-Me	2	—C 2 (Me) 4 —
54	Zr	Cl	2-(2-Fu)	3-Me, 5-Me	3	2-(2-Fu)	3-Me, 5-Me	3	—C 2 (Me) 4 —
55	Zr	Cl	2-(2-Fu)	4-Me, 5-Me	3	2-(2-Fu)	4-Me, 5-Me	3	—C 2 (Me) 4 —
56	Zr	Cl	2-(2-Fu)	4-Et, 5-Me	3	2-(2-Fu)	4-Et, 5-Me	3	—C 2 (Me) 4 —
57	Zr	Cl	2-(2-Fu)	4-(i-Pr), 5-Me	3	2-(2-Fu)	4-(i-Pr), 5-Me	3	—C 2 (Me) 4 —
58	Zr	Cl	2-(2-Fu)	4-(t-Bu), 5-Me	3	2-(2-Fu)	4-(t-Bu), 5-Me	3	—C 2 (Me) 4 —
59	Zr	Cl	2-(2-Fu)	4-Ph, 5-Me	3	2-(2-Fu)	4-Ph, 5-Me	3	—C 2 (Me) 4 —
60	Zr	Cl	2-(2-Fu)	3-Ph, 5-Me	3	2-(2-Fu)	3-Ph, 5-Me	3	—C 2 (Me) 4 —
61	Zr	Cl	2-(2-Fu)	4-Me, 5-Me	3	2-(2-Fu)	4-Me, 5-Me	3	—C 2 (Et) 4 —
62	Zr	Cl	2-(2-Fu)	4-Me, 5-Me	3	2-(2-Fu)	4-Me, 5-Me	3	—C 2 (Ph) 4 —
63	Zr	Me	2-(2-Fu)	4-Me, 5-Me	3	2-(2-Fu)	4-Me, 5-Me	3	—C 2 (Me) 4 —
64	Zr	Bzl	2-(2-Fu)	4-Me, 5-Me	3	2-(2-Fu)	4-Me, 5-Me	3	—C 2 (Me) 4 —
65	Hf	Cl	2-(2-Fu)	4-Me, 5-Me	3	2-(2-Fu)	4-Me, 5-Me	3	—C 2 (Me) 4 —
66	Ti	Cl	2-(2-Fu)	4-Me, 5-Me	3	2-(2-Fu)	4-Me, 5-Me	3	—C 2 (Me) 4 —
67	Hf	Cl	2-(2-Fu)	3-Me, 5-Me	3	2-(2-Fu)	3-Me, 5-Me	3	—C 2 (Me) 4 —
68	Ti	Cl	2-(2-Fu)	3-Me, 5-Me	3	2-(2-Fu)	3-Me, 5-Me	3	—C 2 (Me) 4 —
69	Zr	Cl	2-(3-Fu)	4-Me, 5-Me	3	2-(3-Fu)	4-Me, 5-Me	3	—C 2 (Me) 4 —
70	Zr	Cl	2-(3-Fu)	3-Me, 5-Me	3	2-(3-Fu)	3-Me, 5-Me	3	—C 2 (Me) 4 —
71	Zr	Cl	2-[2-(3-Me—Fu)]	4-Me, 5-Me	3	2-[2-(3-Me—Fu)]	4-Me, 5-Me	3	—C 2 (Me) 4 —
72	Zr	Cl	2-[2-(3-Me—Fu)]	3-Me, 5-Me	3	2-[2-(3-Me—Fu)]	3-Me, 5-Me	3	—C 2 (Me) 4 —
73	Zr	Cl	2-(2-Thie)	4-Me, 5-Me	3	2-(2-Thie)	4-Me, 5-Me	3	—C 2 (Me) 4 —
74	Zr	Cl	2-(2-Thie)	3-Me, 5-Me	3	2-(2-Thie)	3-Me, 5-Me	3	—C 2 (Me) 4 —
75	Zr	Cl	2-(2-Py)	4-Me, 5-Me	3	2-(2-Py)	4-Me, 5-Me	3	—C 2 (Me) 4 —
76	Zr	Cl	2-(2-Py)	3-Me, 5-Me	3	2-(2-Py)	3-Me, 5-Me	3	—C 2 (Me) 4 —
77	Zr	Cl	2-(2-BzFu)	4-Me, 5-Me	3	2-(2-BzFu)	4-Me, 5-Me	3	—C 2 (Me) 4 —
78	Zr	Cl	2-(2-BzFu)	3-Me, 5-Me	3	2-(2-BzFu)	3-Me, 5-Me	3	—C 2 (Me) 4 —
79	Zr	Cl	2-[2-(1-Me—Pyr)]	4-Me, 5-Me	3	2-[2-(1-Me—Pyr)]	4-Me, 5-Me	3	—C 2 (Me) 4 —
80	Zr	Cl	2-[2-(1-Me—Pyr)]	3-Me, 5-Me	3	2-[2-(1-Me—Pyr)]	3-Me, 5-Me	3	—C 2 (Me) 4 —

	TABLE 4
	CA 1 : Cyclopentadienyl	CA 2 : Cyclopentadienyl
No.	M	X	Ra	R 1	p + m	Ra	R 1	q + n	Y
81	Zr	Cl	2-(2-Fu)	—	1	2-(2-Fu)	—	1	—SiH 2 —
82	Zr	Cl	2-(2-Fu)	—	1	2-(2-Fu)	—	1	—Si(Me) 2 —
83	Zr	Cl	2-(2-Fu)	5-Me	2	2-(2-Fu)	5-Me	2	—Si(Me) 2 —
84	Zr	Cl	2-(2-Fu)	4-Me	2	2-(2-Fu)	4-Me	2	—Si(Me) 2 —
85	Zr	Cl	2-(2-Fu)	4-OMe	2	2-(2-Fu)	4-OMe	2	—Si(Me) 2 —
86	Zr	Cl	2-(2-Fu)	4-OPh	2	2-(2-Fu)	4-OPh	2	—Si(Me) 2 —
87	Zr	Cl	2-(2-Fu)	4-Bzl	2	2-(2-Fu)	4-Bzl	2	—Si(Me) 2 —
88	Zr	Cl	2-(2-Fu)	4-Tol	2	2-(2-Fu)	4-Tol	2	—Si(Me) 2 —
89	Zr	Cl	2-(2-Fu)	4-OBzl	2	2-(2-Fu)	4-OBzl	2	—Si(Me) 2 —
90	Zr	Cl	2-(2-Fu)	4-TMS	2	2-(2-Fu)	4-TMS	2	—Si(Me) 2 —
91	Zr	Cl	2-(2-Fu)	4-(1-Pyr)	2	2-(2-Fu)	4-(1-Pyr)	2	—Si(Me) 2 —
92	Zr	Cl	2-(2-Fu)	4-(1-Indo)	2	2-(2-Fu)	4-(1-Indo)	2	—Si(Me) 2 —
93	Zr	Cl	2-(2-Fu)	3-Me	2	2-(2-Fu)	3-Me	2	—Si(Me) 2 —
94	Zr	Cl	2-(2-Fu)	3-Me, 5-Me	3	2-(2-Fu)	3-Me, 5-Me	3	—Si(Me) 2 —
95	Zr	Cl	2-(2-Fu)	4-Me, 5-Me	3	2-(2-Fu)	4-Me, 5-Me	3	—Si(Me) 2 —
96	Zr	Cl	2-(2-Fu)	4-Et, 5-Me	3	2-(2-Fu)	4-Et, 5-Me	3	—Si(Me) 2 —
97	Zr	Cl	2-(2-Fu)	4-(i-Pr), 5-Me	3	2-(2-Fu)	4-(i-Pr), 5-Me	3	—Si(Me) 2 —
98	Zr	Cl	2-(2-Fu)	4-(t-Bu), 5-Me	3	2-(2-Fu)	4-(t-Bu), 5-Me	3	—Si(Me) 2 —
99	Zr	Cl	2-(2-Fu)	4-Ph, 5-Me	3	2-(2-Fu)	4-Ph, 5-Me	3	—Si(Me) 2 —
100	Zr	Cl	2-(2-Fu)	3-Ph, 5-Me	3	2-(2-Fu)	3-Ph, 5-Me	3	—Si(Me) 2 —
101	Zr	Cl	2-(2-Fu)	4-Me, 5-Me	3	2-(2-Fu)	4-Me, 5-Me	3	—Si(Et) 2 —
102	Zr	Cl	2-(2-Fu)	4-Me, 5-Me	3	2-(2-Fu)	4-Me, 5-Me	3	—Si(Ph) 2 —
103	Zr	Me	2-(2-Fu)	4-Me, 5-Me	3	2-(2-Fu)	4-Me, 5-Me	3	—Si(Me) 2 —
104	Zr	Bzl	2-(2-Fu)	4-Me, 5-Me	3	2-(2-Fu)	4-Me, 5-Me	3	—Si(Me) 2 —
105	Hf	Cl	2-(2-Fu)	4-Me, 5-Me	3	2-(2-Fu)	4-Me, 5-Me	3	—Si(Me) 2 —
106	Ti	Cl	2-(2-Fu)	4-Me, 5-Me	3	2-(2-Fu)	4-Me, 5-Me	3	—Si(Me) 2 —
107	Hf	Cl	2-(2-Fu)	3-Me, 5-Me	3	2-(2-Fu)	3-Me, 5-Me	3	—Si(Me) 2 —
108	Ti	Cl	2-(2-Fu)	3-Me, 5-Me	3	2-(2-Fu)	3-Me, 5-Me	3	—Si(Me) 2 —
109	Zr	Cl	2-(3-Fu)	4-Me, 5-Me	3	2-(3-Fu)	4-Me, 5-Me	3	—Si(Me) 2 —
110	Zr	Cl	2-(3-Fu)	3-Me, 5-Me	3	2-(3-Fu)	3-Me, 5-Me	3	—Si(Me) 2 —
111	Zr	Cl	2-[2-(3-Me—Fu)]	4-Me, 5-Me	3	2-[2-(3-Me—Fu)]	4-Me, 5-Me	3	—Si(Me) 2 —
112	Zr	Cl	2-[2-(3-Me—Fu)]	3-Me, 5-Me	3	2-[2-(3-Me—Fu)]	3-Me, 5-Me	3	—Si(Me) 2 —
113	Zr	Cl	2-(2-Thie)	4-Me, 5-Me	3	2-(2-Thie)	4-Me, 5-Me	3	—Si(Me) 2 —
114	Zr	Cl	2-(2-Thie)	3-Me, 5-Me	3	2-(2-Thie)	3-Me, 5-Me	3	—Si(Me) 2 —
115	Zr	Cl	2-(2-Py)	4-Me, 5-Me	3	2-(2-Py)	4-Me, 5-Me	3	—Si(Me) 2 —
116	Zr	Cl	2-(2-Py)	3-Me, 5-Me	3	2-(2-Py)	3-Me, 5-Me	3	—Si(Me) 2 —
117	Zr	Cl	2-(2-BzFu)	4-Me, 5-Me	3	2-(2-BzFu)	4-Me, 5-Me	3	—Si(Me) 2 —
118	Zr	Cl	2-(2-BzFu)	3-Me, 5-Me	3	2-(2-BzFu)	3-Me, 5-Me	3	—Si(Me) 2 —
119	Zr	Cl	2-[2-(N—Me—Pyr)]	4-Me, 5-Me	3	2-[2-(N—Me—Pyr)]	4-Me, 5-Me	3	—Si(Me) 2 —
120	Zr	Cl	2-[2-(N—Me—Pyr)]	3-Me, 5-Me	3	2-[2-(N—Me—Pyr)]	3-Me, 5-Me	3	—Si(Me) 2 —

	TABLE 5
	CA 1 : Cyclopentadienyl	CA 2 : Cyclopentadienyl
No.	M	X	Ra	R 1	p + m	Ra	R 1	q + n	Y
121	Zr	Cl	2-(2-Fu)	—	1	2-(2-Fu)	—	1	—GeH 2 —
122	Zr	Cl	2-(2-Fu)	—	1	2-(2-Fu)	—	1	—Ge(Me) 2 —
123	Zr	Cl	2-(2-Fu)	5-Me	2	2-(2-Fu)	5-Me	2	—Ge(Me) 2 —
124	Zr	Cl	2-(2-Fu)	4-Me	2	2-(2-Fu)	4-Me	2	—Ge(Me) 2 —
125	Zr	Cl	2-(2-Fu)	4-OMe	2	2-(2-Fu)	4-OMe	2	—Ge(Me) 2 —
126	Zr	Cl	2-(2-Fu)	4-OPh	2	2-(2-Fu)	4-OPh	2	—Ge(Me) 2 —
127	Zr	Cl	2-(2-Fu)	4-Bzl	2	2-(2-Fu)	4-Bzl	2	—Ge(Me) 2 —
128	Zr	Cl	2-(2-Fu)	4-Tol	2	2-(2-Fu)	4-Tol	2	—Ge(Me) 2 —
129	Zr	Cl	2-(2-Fu)	4-OBzl	2	2-(2-Fu)	4-OBzl	2	—Ge(Me) 2 —
130	Zr	Cl	2-(2-Fu)	4-TMS	2	2-(2-Fu)	4-TMS	2	—Ge(Me) 2 —
131	Zr	Cl	2-(2-Fu)	4-(1-Pyr)	2	2-(2-Fu)	4-(1-Pyr)	2	—Ge(Me) 2 —
132	Zr	Cl	2-(2-Fu)	4-(1-Indo)	2	2-(2-Fu)	4-(1-Indo)	2	—Ge(Me) 2 —
133	Zr	Cl	2-(2-Fu)	3-Me	2	2-(2-Fu)	3-Me	2	—Ge(Me) 2 —
134	Zr	Cl	2-(2-Fu)	3-Me, 5-Me	3	2-(2-Fu)	3-Me, 5-Me	3	—Ge(Me) 2 —
135	Zr	Cl	2-(2-Fu)	4-Me, 5-Me	3	2-(2-Fu)	4-Me, 5-Me	3	—Ge(Me) 2 —
136	Zr	Cl	2-(2-Fu)	4-Et, 5-Me	3	2-(2-Fu)	4-Et, 5-Me	3	—Ge(Me) 2 —
137	Zr	Cl	2-(2-Fu)	4-(i-Pr), 5-Me	3	2-(2-Fu)	4-(i-Pr), 5-Me	3	—Ge(Me) 2 —
138	Zr	Cl	2-(2-Fu)	4-(t-Bu), 5-Me	3	2-(2-Fu)	4-(t-Bu), 5-Me	3	—Ge(Me) 2 —
139	Zr	Cl	2-(2-Fu)	4-Ph, 5-Me	3	2-(2-Fu)	4-Ph, 5-Me	3	—Ge(Me) 2 —
140	Zr	Cl	2-(2-Fu)	3-Ph, 5-Me	3	2-(2-Fu)	3-Ph, 5-Me	3	—Ge(Me) 2 —
141	Zr	Cl	2-(2-Fu)	4-Me, 5-Me	3	2-(2-Fu)	4-Me, 5-Me	3	—Ge(Et) 2 —
142	Zr	Cl	2-(2-Fu)	4-Me, 5-Me	3	2-(2-Fu)	4-Me, 5-Me	3	—Ge(Ph) 2 —
143	Zr	Me	2-(2-Fu)	4-Me, 5-Me	3	2-(2-Fu)	4-Me, 5-Me	3	—Ge(Me) 2 —
144	Zr	Bzl	2-(2-Fu)	4-Me, 5-Me	3	2-(2-Fu)	4-Me, 5-Me	3	—Ge(Me) 2 —
145	Hf	Cl	2-(2-Fu)	4-Me, 5-Me	3	2-(2-Fu)	4-Me, 5-Me	3	—Ge(Me) 2 —
146	Ti	Cl	2-(2-Fu)	4-Me, 5-Me	3	2-(2-Fu)	4-Me, 5-Me	3	—Ge(Me) 2 —
147	Hf	Cl	2-(2-Fu)	3-Me, 5-Me	3	2-(2-Fu)	3-Me, 5-Me	3	—Ge(Me) 2 —
148	Ti	Cl	2-(2-Fu)	3-Me, 5-Me	3	2-(2-Fu)	3-Me, 5-Me	3	—Ge(Me) 2 —
149	Zr	Cl	2-(3-Fu)	4-Me, 5-Me	3	2-(3-Fu)	4-Me, 5-Me	3	—Ge(Me) 2 —
150	Zr	Cl	2-(3-Fu)	3-Me, 5-Me	3	2-(3-Fu)	3-Me, 5-Me	3	—Ge(Me) 2 —
151	Zr	Cl	2-[2-(3-Me—Fu)]	4-Me, 5-Me	3	2-[2-(3-Me—Fu)]	4-Me, 5-Me	3	—Ge(Me) 2 —
152	Zr	Cl	2-[2-(3-Me—Fu)]	3-Me, 5-Me	3	2-[2-(3-Me—Fu)]	3-Me, 5-Me	3	—Ge(Me) 2 —
153	Zr	Cl	2-(2-Thie)	4-Me, 5-Me	3	2-(2-Thie)	4-Me, 5-Me	3	—Ge(Me) 2 —
154	Zr	Cl	2-(2-Thie)	3-Me, 5-Me	3	2-(2-Thie)	3-Me, 5-Me	3	—Ge(Me) 2 —
155	Zr	Cl	2-(2-Py)	4-Me, 5-Me	3	2-(2-Py)	4-Me, 5-Me	3	—Ge(Me) 2 —
156	Zr	Cl	2-(2-Py)	3-Me, 5-Me	3	2-(2-Py)	3-Me, 5-Me	3	—Ge(Me) 2 —
157	Zr	Cl	2-(2-BzFu)	4-Me, 5-Me	3	2-(2-BzFu)	4-Me, 5-Me	3	—Ge(Me) 2 —
158	Zr	Cl	2-(2-BzFu)	3-Me, 5-Me	3	2-(2-BzFu)	3-Me, 5-Me	3	—Ge(Me) 2 —
159	Zr	Cl	2-[2-(N—Me—Pyr)]	4-Me, 5-Me	3	2-[2-(N—Me—Pyr)]	4-Me, 5-Me	3	—Ge(Me) 2 —
160	Zr	Cl	2-[2-(N—Me—Pyr)]	3-Me, 5-Me	3	2-[2-(N—Me—Pyr)]	3-Me, 5-Me	3	—Ge(Me) 2 —

	TABLE 6
	CA 1 : Cyclopentadienyl	CA 2 : Cyclopentadienyl
No.	M	X	Ra	R 1	p + m	Ra	R 1	q + n	Y
161	Zr	Cl	3-(2-Fu)	—	1	3-(2-Fu)	—	1	—CH 2 —
162	Zr	Cl	3-(2-Fu)	—	1	3-(2-Fu)	—	1	—C(Me) 2 —
163	Zr	Cl	3-(2-Fu)	5-Me	2	3-(2-Fu)	5-Me	2	—C(Me) 2 —
164	Zr	Cl	3-(2-Fu)	4-Me	2	3-(2-Fu)	4-Me	2	—C(Me) 2 —
165	Zr	Cl	3-(2-Fu)	4-OMe	2	3-(2-Fu)	4-OMe	2	—C(Me) 2 —
166	Zr	Cl	3-(2-Fu)	4-OPh	2	3-(2-Fu)	4-OPh	2	—C(Me) 2 —
167	Zr	Cl	3-(2-Fu)	4-Bzl	2	3-(2-Fu)	4-Bzl	2	—C(Me) 2 —
168	Zr	Cl	3-(2-Fu)	4-Tol	2	3-(2-Fu)	4-Tol	2	—C(Me) 2 —
169	Zr	Cl	3-(2-Fu)	4-OBzl	2	3-(2-Fu)	4-OBzl	2	—C(Me) 2 —
170	Zr	Cl	3-(2-Fu)	4-TMS	2	3-(2-Fu)	4-TMS	2	—C(Me) 2 —
171	Zr	Cl	3-(2-Fu)	4-(1-Pyr)	2	3-(2-Fu)	4-(1-Pyr)	2	—C(Me) 2 —
172	Zr	Cl	3-(2-Fu)	4-(1-Indo)	2	3-(2-Fu)	4-(1-Indo)	2	—C(Me) 2 —
173	Zr	Cl	3-(2-Fu)	2-Me	2	3-(2-Fu)	2-Me	2	—C(Me) 2 —
174	Zr	Cl	3-(2-Fu)	2-Me, 5-Me	3	3-(2-Fu)	2-Me, 5-Me	3	—C(Me) 2 —
175	Zr	Cl	3-(2-Fu)	4-Me, 5-Me	3	3-(2-Fu)	4-Me, 5-Me	3	—C(Me) 2 —
176	Zr	Cl	3-(2-Fu)	4-Et, 5-Me	3	3-(2-Fu)	4-Et, 5-Me	3	—C(Me) 2 —
177	Zr	Cl	3-(2-Fu)	4-(i-Pr), 5-Me	3	3-(2-Fu)	4-(i-Pr), 5-Me	3	—C(Me) 2 —
178	Zr	Cl	3-(2-Fu)	4-(t-Bu), 5-Me	3	3-(2-Fu)	4-(t-Bu), 5-Me	3	—C(Me) 2 —
179	Zr	Cl	3-(2-Fu)	4-Ph, 5-Me	3	3-(2-Fu)	4-Ph, 5-Me	3	—C(Me) 2 —
180	Zr	Cl	3-(2-Fu)	2-Ph, 5-Me	3	3-(2-Fu)	2-Ph, 5-Me	3	—C(Me) 2 —
181	Zr	Cl	3-(2-Fu)	4-Me, 5-Me	3	3-(2-Fu)	4-Me, 5-Me	3	—C(Et) 2 —
182	Zr	Cl	3-(2-Fu)	4-Me, 5-Me	3	3-(2-Fu)	4-Me, 5-Me	3	—C(Ph) 2 —
183	Zr	Me	3-(2-Fu)	4-Me, 5-Me	3	3-(2-Fu)	4-Me, 5-Me	3	—C(Me) 2 —
184	Zr	Bzl	3-(2-Fu)	4-Me, 5-Me	3	3-(2-Fu)	4-Me, 5-Me	3	—C(Me) 2 —
185	Hf	Cl	3-(2-Fu)	4-Me, 5-Me	3	3-(2-Fu)	4-Me, 5-Me	3	—C(Me) 2 —
186	Ti	Cl	3-(2-Fu)	4-Me, 5-Me	3	3-(2-Fu)	4-Me, 5-Me	3	—C(Me) 2 —
187	Hf	Cl	3-(2-Fu)	2-Me, 5-Me	3	3-(2-Fu)	2-Me, 5-Me	3	—C(Me) 2 —
188	Ti	Cl	3-(2-Fu)	2-Me, 5-Me	3	3-(2-Fu)	2-Me, 5-Me	3	—C(Me) 2 —
189	Zr	Cl	3-(3-Fu)	4-Me, 5-Me	3	3-(3-Fu)	4-Me, 5-Me	3	—C(Me) 2 —
190	Zr	Cl	3-(3-Fu)	2-Me, 5-Me	3	3-(3-Fu)	2-Me, 5-Me	3	—C(Me) 2 —
191	Zr	Cl	3-[2-(3-Me—Fu)]	4-Me, 5-Me	3	3-[2-(3-Me—Fu)]	4-Me, 5-Me	3	—C(Me) 2 —
192	Zr	Cl	3-[2-(3-Me—Fu)]	2-Me, 5-Me	3	3-[2-(3-Me—Fu)]	2-Me, 5-Me	3	—C(Me) 2 —
193	Zr	Cl	3-(2-Thie)	4-Me, 5-Me	3	3-(2-Thie)	4-Me, 5-Me	3	—C(Me) 2 —
194	Zr	Cl	3-(2-Thie)	2-Me, 5-Me	3	3-(2-Thie)	2-Me, 5-Me	3	—C(Me) 2 —
195	Zr	Cl	3-(2-Py)	4-Me, 5-Me	3	3-(2-Py)	4-Me, 5-Me	3	—C(Me) 2 —
196	Zr	Cl	3-(2-Py)	2-Me, 5-Me	3	3-(2-Py)	2-Me, 5-Me	3	—C(Me) 2 —
197	Zr	Cl	3-(2-BzFu)	4-Me, 5-Me	3	3-(2-BzFu)	4-Me, 5-Me	3	—C(Me) 2 —
198	Zr	Cl	3-(2-BzFu)	2-Me, 5-Me	3	3-(2-BzFu)	2-Me, 5-Me	3	—C(Me) 2 —
199	Zr	Cl	3-[2-(N—Me—Pyr)]	4-Me, 5-Me	3	3-[2-(N—Me—Pyr)]	4-Me, 5-Me	3	—C(Me) 2 —
200	Zr	Cl	3-[2-(N—Me—Pyr)]	2-Me, 5-Me	3	3-[2-(N—Me—Pyr)]	2-Me, 5-Me	3	—C(Me) 2 —

	TABLE 7
	CA 1 : Cyclopentadienyl	CA 2 : Cyclopentadienyl
No.	M	X	Ra	R 1	p + m	Ra	R 1	q + n	Y
201	Zr	Cl	3-(2-Fu)	—	1	3-(2-Fu)	—	1	—CH 2 CH 2 —
202	Zr	Cl	3-(2-Fu)	—	1	3-(2-Fu)	—	1	—C 2 (Me) 4 —
203	Zr	Cl	3-(2-Fu)	5-Me	2	3-(2-Fu)	5-Me	2	—C 2 (Me) 4 —
204	Zr	Cl	3-(2-Fu)	4-Me	2	3-(2-Fu)	4-Me	2	—C 2 (Me) 4 —
205	Zr	Cl	3-(2-Fu)	4-OMe	2	3-(2-Fu)	4-OMe	2	—C 2 (Me) 4 —
206	Zr	Cl	3-(2-Fu)	4-OPh	2	3-(2-Fu)	4-OPh	2	—C 2 (Me) 4 —
207	Zr	Cl	3-(2-Fu)	4-Bzl	2	3-(2-Fu)	4-Bzl	2	—C 2 (Me) 4 —
208	Zr	Cl	3-(2-Fu)	4-Tol	2	3-(2-Fu)	4-Tol	2	—C 2 (Me) 4 —
209	Zr	Cl	3-(2-Fu)	4-OBzl	2	3-(2-Fu)	4-OBzl	2	—C 2 (Me) 4 —
210	Zr	Cl	3-(2-Fu)	4-TMS	2	3-(2-Fu)	4-TMS	2	—C 2 (Me) 4 —
211	Zr	Cl	3-(2-Fu)	4-(1-Pyr)	2	3-(2-Fu)	4-(1-Pyr)	2	—C 2 (Me) 4 —
212	Zr	Cl	3-(2-Fu)	4-(1-Indo)	2	3-(2-Fu)	4-(1-Indo)	2	—C 2 (Me) 4 —
213	Zr	Cl	3-(2-Fu)	2-Me	2	3-(2-Fu)	2-Me	2	—C 2 (Me) 4 —
214	Zr	Cl	3-(2-Fu)	2-Me, 5-Me	3	3-(2-Fu)	2-Me, 5-Me	3	—C 2 (Me) 4 —
215	Zr	Cl	3-(2-Fu)	4-Me, 5-Me	3	3-(2-Fu)	4-Me, 5-Me	3	—C 2 (Me) 4 —
216	Zr	Cl	3-(2-Fu)	4-Et, 5-Me	3	3-(2-Fu)	4-Et, 5-Me	3	—C 2 (Me) 4 —
217	Zr	Cl	3-(2-Fu)	4-(i-Pr), 5-Me	3	3-(2-Fu)	4-(i-Pr), 5-Me	3	—C 2 (Me) 4 —
218	Zr	Cl	3-(2-Fu)	4-(t-Bu), 5-Me	3	3-(2-Fu)	4-(t-Bu), 5-Me	3	—C 2 (Me) 4 —
219	Zr	Cl	3-(2-Fu)	4-Ph, 5-Me	3	3-(2-Fu)	4-Ph, 5-Me	3	—C 2 (Me) 4 —
220	Zr	Cl	3-(2-Fu)	2-Ph, 5-Me	3	3-(2-Fu)	2-Ph, 5-Me	3	—C 2 (Me) 4 —
221	Zr	Cl	3-(2-Fu)	4-Me, 5-Me	3	3-(2-Fu)	4-Me, 5-Me	3	—C 2 (Et) 4 —
222	Zr	Cl	3-(2-Fu)	4-Me, 5-Me	3	3-(2-Fu)	4-Me, 5-Me	3	—C 2 (Ph) 4 —
223	Zr	Me	3-(2-Fu)	4-Me, 5-Me	3	3-(2-Fu)	4-Me, 5-Me	3	—C 2 (Me) 4 —
224	Zr	Bzl	3-(2-Fu)	4-Me, 5-Me	3	3-(2-Fu)	4-Me, 5-Me	3	—C 2 (Me) 4 —
225	Hf	Cl	3-(2-Fu)	4-Me, 5-Me	3	3-(2-Fu)	4-Me, 5-Me	3	—C 2 (Me) 4 —
226	Ti	Cl	3-(2-Fu)	4-Me, 5-Me	3	3-(2-Fu)	4-Me, 5-Me	3	—C 2 (Me) 4 —
227	Hf	Cl	3-(2-Fu)	2-Me, 5-Me	3	3-(2-Fu)	2-Me, 5-Me	3	—C 2 (Me) 4 —
228	Ti	Cl	3-(2-Fu)	2-Me, 5-Me	3	3-(2-Fu)	2-Me, 5-Me	3	—C 2 (Me) 4 —
229	Zr	Cl	3-(3-Fu)	4-Me, 5-Me	3	3-(3-Fu)	4-Me, 5-Me	3	—C 2 (Me) 4 —
230	Zr	Cl	3-(3-Fu)	2-Me, 5-Me	3	3-(3-Fu)	2-Me, 5-Me	3	—C 2 (Me) 4 —
231	Zr	Cl	3-[2-(3-Me—Fu)]	4-Me, 5-Me	3	3-[2-(3-Me—Fu)]	4-Me, 5-Me	3	—C 2 (Me) 4 —
232	Zr	Cl	3-[2-(3-Me—Fu)]	2-Me, 5-Me	3	3-[2-(3-Me—Fu)]	2-Me, 5-Me	3	—C 2 (Me) 4 —
233	Zr	Cl	3-(2-Thie)	4-Me, 5-Me	3	3-(2-Thie)	4-Me, 5-Me	3	—C 2 (Me) 4 —
234	Zr	Cl	3-(2-Thie)	2-Me, 5-Me	3	3-(2-Thie)	2-Me, 5-Me	3	—C 2 (Me) 4 —
235	Zr	Cl	3-(2-Py)	4-Me, 5-Me	3	3-(2-Py)	4-Me, 5-Me	3	—C 2 (Me) 4 —
236	Zr	Cl	3-(2-Py)	2-Me, 5-Me	3	3-(2-Py)	2-Me, 5-Me	3	—C 2 (Me) 4 —
237	Zr	Cl	3-(2-BzFu)	4-Me, 5-Me	3	3-(2-BzFu)	4-Me, 5-Me	3	—C 2 (Me) 4 —
238	Zr	Cl	3-(2-BzFu)	2-Me, 5-Me	3	3-(2-BzFu)	2-Me, 5-Me	3	—C 2 (Me) 4 —
239	Zr	Cl	3-[2-(N—Me—Pyr)]	4-Me, 5-Me	3	3-[2-(N—Me—Pyr)]	4-Me, 5-Me	3	—C 2 (Me) 4 —
240	Zr	Cl	3-[2-(N—Me—Pyr)]	2-Me, 5-Me	3	3-[2-(N—Me—Pyr)]	2-Me, 5-Me	3	—C 2 (Me) 4 —

	TABLE 8
	CA 1 : Cyclopentadienyl	CA 2 : Cyclopentadienyl
No.	M	X	Ra	R 1	p + m	Ra	R 1	q + n	Y
241	Zr	Cl	3-(2-Fu)	—	1	3-(2-Fu)	—	1	—SiH 2 —
242	Zr	Cl	3-(2-Fu)	—	1	3-(2-Fu)	—	1	—Si(Me) 2 —
243	Zr	Cl	3-(2-Fu)	5-Me	2	3-(2-Fu)	5-Me	2	—Si(Me) 2 —
244	Zr	Cl	3-(2-Fu)	4-Me	2	3-(2-Fu)	4-Me	2	—Si(Me) 2 —
245	Zr	Cl	3-(2-Fu)	4-OMe	2	3-(2-Fu)	4-OMe	2	—Si(Me) 2 —
246	Zr	Cl	3-(2-Fu)	4-OPh	2	3-(2-Fu)	4-OPh	2	—Si(Me) 2 —
247	Zr	Cl	3-(2-Fu)	4-Bzl	2	3-(2-Fu)	4-Bzl	2	—Si(Me) 2 —
248	Zr	Cl	3-(2-Fu)	4-Tol	2	3-(2-Fu)	4-Tol	2	—Si(Me) 2 —
249	Zr	Cl	3-(2-Fu)	4-OBzl	2	3-(2-Fu)	4-OBzl	2	—Si(Me) 2 —
250	Zr	Cl	3-(2-Fu)	4-TMS	2	3-(2-Fu)	4-TMS	2	—Si(Me) 2 —
251	Zr	Cl	3-(2-Fu)	4-(1-Pyr)	2	3-(2-Fu)	4-(1-Pyr)	2	—Si(Me) 2 —
252	Zr	Cl	3-(2-Fu)	4-(1-Indo)	2	3-(2-Fu)	4-(1-Indo)	2	—Si(Me) 2 —
253	Zr	Cl	3-(2-Fu)	2-Me	2	3-(2-Fu)	2-Me	2	—Si(Me) 2 —
254	Zr	Cl	3-(2-Fu)	2-Me, 5-Me	3	3-(2-Fu)	2-Me, 5-Me	3	—Si(Me) 2 —
255	Zr	Cl	3-(2-Fu)	4-Me, 5-Me	3	3-(2-Fu)	4-Me, 5-Me	3	—Si(Me) 2 —
256	Zr	Cl	3-(2-Fu)	4-Et, 5-Me	3	3-(2-Fu)	4-Et, 5-Me	3	—Si(Me) 2 —
257	Zr	Cl	3-(2-Fu)	4-(i-Pr), 5-Me	3	3-(2-Fu)	4-(i-Pr), 5-Me	3	—Si(Me) 2 —
258	Zr	Cl	3-(2-Fu)	4-(t-Bu), 5-Me	3	3-(2-Fu)	4-(t-Bu), 5-Me	3	—Si(Me) 2 —
259	Zr	Cl	3-(2-Fu)	4-Ph, 5-Me	3	3-(2-Fu)	4-Ph, 5-Me	3	—Si(Me) 2 —
260	Zr	Cl	3-(2-Fu)	2-Ph, 5-Me	3	3-(2-Fu)	2-Ph, 5-Me	3	—Si(Me) 2 —
261	Zr	Cl	3-(2-Fu)	4-Me, 5-Me	3	3-(2-Fu)	4-Me, 5-Me	3	—Si(Et) 2 —
262	Zr	Cl	3-(2-Fu)	4-Me, 5-Me	3	3-(2-Fu)	4-Me, 5-Me	3	—Si(Ph) 2 —
263	Zr	Me	3-(2-Fu)	4-Me, 5-Me	3	3-(2-Fu)	4-Me, 5-Me	3	—Si(Me) 2 —
264	Zr	Bzl	3-(2-Fu)	4-Me, 5-Me	3	3-(2-Fu)	4-Me, 5-Me	3	—Si(Me) 2 —
265	Hf	Cl	3-(2-Fu)	4-Me, 5-Me	3	3-(2-Fu)	4-Me, 5-Me	3	—Si(Me) 2 —
266	Ti	Cl	3-(2-Fu)	4-Me, 5-Me	3	3-(2-Fu)	4-Me, 5-Me	3	—Si(Me) 2 —
267	Hf	Cl	3-(2-Fu)	2-Me, 5-Me	3	3-(2-Fu)	2-Me, 5-Me	3	—Si(Me) 2 —
268	Ti	Cl	3-(2-Fu)	2-Me, 5-Me	3	3-(2-Fu)	2-Me, 5-Me	3	—Si(Me) 2 —
269	Zr	Cl	3-(3-Fu)	4-Me, 5-Me	3	3-(3-Fu)	4-Me, 5-Me	3	—Si(Me) 2 —
270	Zr	Cl	3-(3-Fu)	2-Me, 5-Me	3	3-(3-Fu)	2-Me, 5-Me	3	—Si(Me) 2 —
271	Zr	Cl	3-[2-(3-Me—Fu)]	4-Me, 5-Me	3	3-[2-(3-Me—Fu)]	4-Me, 5-Me	3	—Si(Me) 2 —
272	Zr	Cl	3-[2-(3-Me—Fu)]	2-Me, 5-Me	3	3-[2-(3-Me—Fu)]	2-Me, 5-Me	3	—Si(Me) 2 —
273	Zr	Cl	3-(2-Thie)	4-Me, 5-Me	3	3-(2-Thie)	4-Me, 5-Me	3	—Si(Me) 2 —
274	Zr	Cl	3-(2-Thie)	2-Me, 5-Me	3	3-(2-Thie)	2-Me, 5-Me	3	—Si(Me) 2 —
275	Zr	Cl	3-(2-Py)	4-Me, 5-Me	3	3-(2-Py)	4-Me, 5-Me	3	—Si(Me) 2 —
276	Zr	Cl	3-(2-Py)	2-Me, 5-Me	3	3-(2-Py)	2-Me, 5-Me	3	—Si(Me) 2 —
277	Zr	Cl	3-(2-BzFu)	4-Me, 5-Me	3	3-(2-BzFu)	4-Me, 5-Me	3	—Si(Me) 2 —
278	Zr	Cl	3-(2-BzFu)	2-Me, 5-Me	3	3-(2-BzFu)	2-Me, 5-Me	3	—Si(Me) 2 —
279	Zr	Cl	3-[2-(N—Me—Pyr)]	4-Me, 5-Me	3	3-[2-(N—Me—Pyr)]	4-Me, 5-Me	3	—Si(Me) 2 —
280	Zr	Cl	3-[2-(N—Me—Pyr)]	2-Me, 5-Me	3	3-[2-(N—Me—Pyr)]	2-Me, 5-Me	3	—Si(Me) 2 —

	TABLE 9
	CA 1 : Cyclopentadienyl	CA 2 : Cyclopentadienyl
No.	M	X	Ra	R 1	p + m	Ra	R 1	q + n	Y
281	Zr	Cl	3-(2-Fu)	—	1	3-(2-Fu)	—	1	—GeH 2 —
282	Zr	Cl	3-(2-Fu)	—	1	3-(2-Fu)	—	1	—Ge(Me) 2 —
283	Zr	Cl	3-(2-Fu)	5-Me	2	3-(2-Fu)	5-Me	2	—Ge(Me) 2 —
284	Zr	Cl	3-(2-Fu)	4-Me	2	3-(2-Fu)	4-Me	2	—Ge(Me) 2 —
285	Zr	Cl	3-(2-Fu)	4-OMe	2	3-(2-Fu)	4-OMe	2	—Ge(Me) 2 —
286	Zr	Cl	3-(2-Fu)	4-OPh	2	3-(2-Fu)	4-OPh	2	—Ge(Me) 2 —
287	Zr	Cl	3-(2-Fu)	4-Bzl	2	3-(2-Fu)	4-Bzl	2	—Ge(Me) 2 —
288	Zr	Cl	3-(2-Fu)	4-Tol	2	3-(2-Fu)	4-Tol	2	—Ge(Me) 2 —
289	Zr	Cl	3-(2-Fu)	4-OBzl	2	3-(2-Fu)	4-OBzl	2	—Ge(Me) 2 —
290	Zr	Cl	3-(2-Fu)	4-TMS	2	3-(2-Fu)	4-TMS	2	—Ge(Me) 2 —
291	Zr	Cl	3-(2-Fu)	4-(1-Pyr)	2	3-(2-Fu)	4-(1-Pyr)	2	—Ge(Me) 2 —
292	Zr	Cl	3-(2-Fu)	4-(1-Indo)	2	3-(2-Fu)	4-(1-Indo)	2	—Ge(Me) 2 —
293	Zr	Cl	3-(2-Fu)	2-Me	2	3-(2-Fu)	2-Me	2	—Ge(Me) 2 —
294	Zr	Cl	3-(2-Fu)	2-Me, 5-Me	3	3-(2-Fu)	2-Me, 5-Me	3	—Ge(Me) 2 —
295	Zr	Cl	3-(2-Fu)	4-Me, 5-Me	3	3-(2-Fu)	4-Me, 5-Me	3	—Ge(Me) 2 —
296	Zr	Cl	3-(2-Fu)	4-Et, 5-Me	3	3-(2-Fu)	4-Et, 5-Me	3	—Ge(Me) 2 —
297	Zr	Cl	3-(2-Fu)	4-(i-Pr), 5-Me	3	3-(2-Fu)	4-(i-Pr), 5-Me	3	—Ge(Me) 2 —
298	Zr	Cl	3-(2-Fu)	4-(t-Bu), 5-Me	3	3-(2-Fu)	4-(t-Bu), 5-Me	3	—Ge(Me) 2 —
299	Zr	Cl	3-(2-Fu)	4-Ph, 5-Me	3	3-(2-Fu)	4-Ph, 5-Me	3	—Ge(Me) 2 —
300	Zr	Cl	3-(2-Fu)	2-Ph, 5-Me	3	3-(2-Fu)	2-Ph, 5-Me	3	—Ge(Me) 2 —
301	Zr	Cl	3-(2-Fu)	4-Me, 5-Me	3	3-(2-Fu)	4-Me, 5-Me	3	—Ge(Et) 2 —
302	Zr	Cl	3-(2-Fu)	4-Me, 5-Me	3	3-(2-Fu)	4-Me, 5-Me	3	—Ge(Ph) 2 —
303	Zr	Me	3-(2-Fu)	4-Me, 5-Me	3	3-(2-Fu)	4-Me, 5-Me	3	—Ge(Me) 2 —
304	Zr	Bzl	3-(2-Fu)	4-Me, 5-Me	3	3-(2-Fu)	4-Me, 5-Me	3	—Ge(Me) 2 —
305	Hf	Cl	3-(2-Fu)	4-Me, 5-Me	3	3-(2-Fu)	4-Me, 5-Me	3	—Ge(Me) 2 —
306	Ti	Cl	3-(2-Fu)	4-Me, 5-Me	3	3-(2-Fu)	4-Me, 5-Me	3	—Ge(Me) 2 —
307	Hf	Cl	3-(2-Fu)	2-Me, 5-Me	3	3-(2-Fu)	2-Me, 5-Me	3	—Ge(Me) 2 —
308	Ti	Cl	3-(2-Fu)	2-Me, 5-Me	3	3-(2-Fu)	2-Me, 5-Me	3	—Ge(Me) 2 —
309	Zr	Cl	3-(3-Fu)	4-Me, 5-Me	3	3-(3-Fu)	4-Me, 5-Me	3	—Ge(Me) 2 —
310	Zr	Cl	3-(3-Fu)	2-Me, 5-Me	3	3-(3-Fu)	2-Me, 5-Me	3	—Ge(Me) 2 —
311	Zr	Cl	3-[2-(3-Me—Fu)]	4-Me, 5-Me	3	3-[2-(3-Me—Fu)]	4-Me, 5-Me	3	—Ge(Me) 2 —
312	Zr	Cl	3-[2-(3-Me—Fu)]	2-Me, 5-Me	3	3-[2-(3-Me—Fu)]	2-Me, 5-Me	3	—Ge(Me) 2 —
313	Zr	Cl	3-(2-Thie)	4-Me, 5-Me	3	3-(2-Thie)	4-Me, 5-Me	3	—Ge(Me) 2 —
314	Zr	Cl	3-(2-Thie)	2-Me, 5-Me	3	3-(2-Thie)	2-Me, 5-Me	3	—Ge(Me) 2 —
315	Zr	Cl	3-(2-Py)	4-Me, 5-Me	3	3-(2-Py)	4-Me, 5-Me	3	—Ge(Me) 2 —
316	Zr	Cl	3-(2-Py)	2-Me, 5-Me	3	3-(2-Py)	2-Me, 5-Me	3	—Ge(Me) 2 —
317	Zr	Cl	3-(2-BzFu)	4-Me, 5-Me	3	3-(2-BzFu)	4-Me, 5-Me	3	—Ge(Me) 2 —
318	Zr	Cl	3-(2-BzFu)	2-Me, 5-Me	3	3-(2-BzFu)	2-Me, 5-Me	3	—Ge(Me) 2 —
319	Zr	Cl	3-[2-(N—Me—Pyr)]	4-Me, 5-Me	3	3-[2-(N—Me—Pyr)]	4-Me, 5-Me	3	—Ge(Me) 2 —
320	Zr	Cl	3-[2-(N—Me—Pyr)]	2-Me, 5-Me	3	3-[2-(N—Me—Pyr)]	2-Me, 5-Me	3	—Ge(Me) 2 —

	TABLE 10
	CA 1 : Indenyl	CA 2 : Indenyl
No.	M	X	Ra	R 1	p + m	Ra	R 1	q + n	Y
321	Zr	Cl	2-(2-Fu)	—	1	2-(2-Fu)	—	1	—CH 2 —
322	Zr	Cl	2-(2-Fu)	—	1	2-(2-Fu)	—	1	—C(Me) 2 —
323	Zr	Cl	2-(2-Fu)	7-Me	2	2-(2-Fu)	7-Me	2	—C(Me) 2 —
324	Zr	Cl	2-(2-Fu)	4-Me	2	2-(2-Fu)	4-Me	2	—C(Me) 2 —
325	Zr	Cl	2-(2-Fu)	3-Me	2	2-(2-Fu)	3-Me	2	—C(Me) 2 —
326	Zr	Cl	2-(2-Fu)	3-Me, 7-Me	3	2-(2-Fu)	3-Me, 7-Me	3	—C(Me) 2 —
327	Zr	Cl	2-(2-Fu)	4-Me, 7-Me	3	2-(2-Fu)	4-Me, 7-Me	3	—C(Me) 2 —
328	Zr	Cl	2-(2-Fu)	4-Cl	2	2-(2-Fu)	4-Cl	2	—C(Me) 2 —
329	Zr	Cl	2-(2-Fu)	4-Et	2	2-(2-Fu)	4-Et	2	—C(Me) 2 —
330	Zr	Cl	2-(2-Fu)	4-i-Pr	2	2-(2-Fu)	4-i-Pr	2	—C(Me) 2 —
331	Zr	Cl	2-(2-Fu)	4-t-Bu	2	2-(2-Fu)	4-t-Bu	2	—C(Me) 2 —
332	Zr	Cl	2-(2-Fu)	4-Ph	2	2-(2-Fu)	4-Ph	2	—C(Me) 2 —
333	Zr	Cl	2-(2-Fu)	4-Np	2	2-(2-Fu)	4-Np	2	—C(Me) 2 —
334	Zr	Cl	2-(2-Fu)	4-OMe	2	2-(2-Fu)	4-OMe	2	—C(Me) 2 —
335	Zr	Cl	2-(2-Fu)	4-OPh	2	2-(2-Fu)	4-OPh	2	—C(Me) 2 —
336	Zr	Cl	2-(2-Fu)	4-Bzl	2	2-(2-Fu)	4-Bzl	2	—C(Me) 2 —
337	Zr	Cl	2-(2-Fu)	4-Tol	2	2-(2-Fu)	4-Tol	2	—C(Me) 2 —
338	Zr	Cl	2-(2-Fu)	4-OBzl	2	2-(2-Fu)	4-OBzl	2	—C(Me) 2 —
339	Zr	Cl	2-(2-Fu)	4-TMS	2	2-(2-Fu)	4-TMS	2	—C(Me) 2 —
340	Zr	Cl	2-(2-Fu)	4-(1-Pyr)	2	2-(2-Fu)	4-(1-Pyr)	2	—C(Me) 2 —
341	Zr	Cl	2-(2-Fu)	4-(1-Indo)	2	2-(2-Fu)	4-(1-Indo)	2	—C(Et) 2 —
342	Zr	Cl	2-(2-Fu), 4-(2-Fu)	—	2	2-(2-Fu), 4-(2-Fu)	—	2	—C(Ph) 2 —
343	Zr	Cl	2-(2-Fu), 4-(2-Thie)	—	2	2-(2-Fu), 4-(2-Thie)	—	2	—C(Me) 2 —
344	Zr	Cl	2-(2-Fu), 4-(2-BzFu)	—	2	2-(2-Fu), 4-(2-BzFu)	—	2	—C(Me) 2 —
345	Zr	Cl	2-(2-Fu), 4-(2-Py)	—	2	2-(2-Fu), 4-(2-Py)	—	2	—C(Me) 2 —
346	Zr	Cl	2-(2-Fu), 4-(1-MePyr)	—	2	2-(2-Fu), 4-(1-MePyr)	—	2	—C(Me) 2 —
347	Zr	Cl	2-(2-Fu)	4-Et, 7-Et	3	2-(2-Fu)	4-Et, 7-Et	3	—C(Me) 2 —
348	Zr	Cl	2-(2-Fu)	4-i-Pr, 7-i-Pr	3	2-(2-Fu)	4-i-Pr, 7-i-Pr	3	—C(Me) 2 —
349	Zr	Cl	2-(2-Fu)	4-t-Bu, 7-t-Bu	3	2-(2-Fu)	4-t-Bu, 7-t-Bu	3	—C(Me) 2 —
350	Zr	Cl	2-(2-Fu)	4-Ph, 7-Ph	3	2-(2-Fu)	4-Ph, 7-Ph	3	—C(Me) 2 —
351	Zr	Cl	2-(2-Fu)	3-Ph, 7-Me	3	2-(2-Fu)	3-Ph, 7-Me	3	—C(Me) 2 —
352	Zr	Cl	2-(2-Fu)	4-Me, 7-Me	3	2-(2-Fu)	4-Me, 7-Me	3	—C(Et) 2 —
353	Zr	Cl	2-(2-Fu)	4-Me, 7-Me	3	2-(2-Fu)	4-Me, 7-Me	3	—C(Ph) 2 —
354	Zr	Me	2-(2-Fu)	4-Ph	2	2-(2-Fu)	4-Ph	2	—C(Me) 2 —
355	Zr	Bzl	2-(2-Fu)	4-Ph	2	2-(2-Fu)	4-Ph	2	—C(Me) 2 —
356	Hf	Cl	2-(2-Fu)	4-Ph	2	2-(2-Fu)	4-Ph	2	—C(Me) 2 —
357	Ti	Cl	2-(2-Fu)	4-Ph	2	2-(2-Fu)	4-Ph	2	—C(Me) 2 —
358	Hf	Cl	2-(2-Fu)	3-Me, 7-Me	3	2-(2-Fu)	3-Me, 7-Me	3	—C(Me) 2 —
359	Ti	Cl	2-(2-Fu)	3-Me, 7-Me	3	2-(2-Fu)	3-Me, 7-Me	3	—C(Me) 2 —
360	Zr	Cl	2-(3-Fu)	4-Ph	2	2-(3-Fu)	4-Ph	2	—C(Me) 2 —
361	Zr	Cl	2-(3-Fu)	4-Ph	2	2-(3-Fu)	4-Ph	2	—C(Me) 2 —
362	Zr	Cl	2-[2-(3-Me—Fu)]	4-Ph	2	2-[2-(3-Me—Fu)]	4-Ph	2	—C(Me) 2 —
363	Zr	Cl	2-[2-(3-Me—Fu)]	—	1	2-[2-(3-Me—Fu)]	—	1	—C(Me) 2 —
364	Zr	Cl	2-(2-Thie)	4-Ph	2	2-(2-Thie)	4-Ph	2	—C(Me) 2 —
365	Zr	Cl	2-(2-Thie)	—	1	2-(2-Thie)	—	1	—C(Me) 2 —
366	Zr	Cl	2-(2-Py)	4-Ph	2	2-(2-Py)	4-Ph	2	—C(Me) 2 —
367	Zr	Cl	2-(2-Py)	—	1	2-(2-Py)	—	1	—C(Me) 2 —
368	Zr	Cl	2-(2-BzFu)	4-Ph	2	2-(2-BzFu)	4-Ph	2	—C(Me) 2 —
369	Zr	Cl	2-(2-BzFu)	—	1	2-(2-BzFu)	—	1	—C(Me) 2 —
370	Zr	Cl	2-[2-(1-Me—Pyr)]	4-Ph	2	2-[2-(1-Me—Pyr)]	4-Ph	2	—C(Me) 2 —
371	Zr	Cl	2-[2-(1-Me—Pyr)]	—	1	2-[2-(1-Me—Pyr)]	—	1	—C(Me) 2 —

	TABLE 11
	CA 1 : Indenyl	CA 2 : Indenyl
No.	M	X	Ra	R 1	p + m	Ra	R 1	q + n	Y
372	Zr	Cl	2-(2-Fu)	—	1	2-(2-Fu)	—	1	—CH 2 CH 2 —
373	Zr	Cl	2-(2-Fu)	—	1	2-(2-Fu)	—	1	—C 2 (Me) 4 —
374	Zr	Cl	2-(2-Fu)	7-Me	2	2-(2-Fu)	7-Me	2	—C 2 (Me) 4 —
375	Zr	Cl	2-(2-Fu)	4-Me	2	2-(2-Fu)	4-Me	2	—C 2 (Me) 4 —
376	Zr	Cl	2-(2-Fu)	3-Me	2	2-(2-Fu)	3-Me	2	—C 2 (Me) 4 —
377	Zr	Cl	2-(2-Fu)	3-Me, 7-Me	3	2-(2-Fu)	3-Me, 7-Me	3	—C 2 (Me) 4 —
378	Zr	Cl	2-(2-Fu)	4-Me, 7-Me	3	2-(2-Fu)	4-Me, 7-Me	3	—C 2 (Me) 4 —
379	Zr	Cl	2-(2-Fu)	4-Cl	2	2-(2-Fu)	4-Cl	2	—C 2 (Me) 4 —
380	Zr	Cl	2-(2-Fu)	4-Et	2	2-(2-Fu)	4-Et	2	—C 2 (Me) 4 —
381	Zr	Cl	2-(2-Fu)	4-i-Pr	2	2-(2-Fu)	4-i-Pr	2	—C 2 (Me) 4 —
382	Zr	Cl	2-(2-Fu)	4-t-Bu	2	2-(2-Fu)	4-t-Bu	2	—C 2 (Me) 4 —
383	Zr	Cl	2-(2-Fu)	4-Ph	2	2-(2-Fu)	4-Ph	2	—C 2 (Me) 4 —
384	Zr	Cl	2-(2-Fu)	4-Np	2	2-(2-Fu)	4-Np	2	—C 2 (Me) 4 —
385	Zr	Cl	2-(2-Fu)	4-OMe	2	2-(2-Fu)	4-OMe	2	—C 2 (Me) 4 —
386	Zr	Cl	2-(2-Fu)	4-OPh	2	2-(2-Fu)	4-OPh	2	—C 2 (Me) 4 —
387	Zr	Cl	2-(2-Fu)	4-Bzl	2	2-(2-Fu)	4-Bzl	2	—C 2 (Me) 4 —
388	Zr	Cl	2-(2-Fu)	4-Tol	2	2-(2-Fu)	4-Tol	2	—C 2 (Me) 4 —
389	Zr	Cl	2-(2-Fu)	4-OBzl	2	2-(2-Fu)	4-OBzl	2	—C 2 (Me) 4 —
390	Zr	Cl	2-(2-Fu)	4-TMS	2	2-(2-Fu)	4-TMS	2	—C 2 (Me) 4 —
391	Zr	Cl	2-(2-Fu)	4-(1-Pyr)	2	2-(2-Fu)	4-(1-Pyr)	2	—C 2 (Me) 4 —
392	Zr	Cl	2-(2-Fu)	4-(1-Indo)	2	2-(2-Fu)	4-(1-Indo)	2	—C 2 (Me) 4 —
393	Zr	Cl	2-(2-Fu), 4-(2-Fu)	—	2	2-(2-Fu), 4-(2-Fu)	—	2	—C 2 (Me) 4 —
394	Zr	Cl	2-(2-Fu), 4-(2-Thie)	—	2	2-(2-Fu), 4-(2-Thie)	—	2	—C 2 (Me) 4 —
395	Zr	Cl	2-(2-Fu), 4-(2-BzFu)	—	2	2-(2-Fu), 4-(2-BzFu)	—	2	—C 2 (Me) 4 —
396	Zr	Cl	2-(2-Fu), 4-(2-Py)	—	2	2-(2-Fu), 4-(2-Py)	—	2	—C 2 (Me) 4 —
397	Zr	Cl	2-(2-Fu), 4-(1-MePyr)	—	2	2-(2-Fu), 4-(1-MePyr)	—	2	—C 2 (Me) 4 —
398	Zr	Cl	2-(2-Fu)	4-Et, 7-Et	3	2-(2-Fu)	4-Et, 7-Et	3	—C 2 (Me) 4 —
399	Zr	Cl	2-(2-Fu)	4-i-Pr, 7-i-Pr	3	2-(2-Fu)	4-i-Pr, 7-i-Pr	3	—C 2 (Me) 4 —
400	Zr	Cl	2-(2-Fu)	4-t-Bu, 7-t-Bu	3	2-(2-Fu)	4-t-Bu, 7-t-Bu	3	—C 2 (Me) 4 —
401	Zr	Cl	2-(2-Fu)	4-Ph, 7-Ph	3	2-(2-Fu)	4-Ph, 7-Ph	3	—C 2 (Me) 4 —
402	Zr	Cl	2-(2-Fu)	3-Ph, 7-Me	3	2-(2-Fu)	3-Ph, 7-Me	3	—C 2 (Me) 4 —
403	Zr	Cl	2-(2-Fu)	4-Me, 7-Me	3	2-(2-Fu)	4-Me, 7-Me	3	—C 2 (Et) 4 —
404	Zr	Cl	2-(2-Fu)	4-Me, 7-Me	3	2-(2-Fu)	4-Me, 7-Me	3	—C 2 (Ph) 4 —
405	Zr	Me	2-(2-Fu)	4-Ph	2	2-(2-Fu)	4-Ph	2	—C 2 (Me) 4 —
406	Zr	Bzl	2-(2-Fu)	4-Ph	2	2-(2-Fu)	4-Ph	2	—C 2 (Me) 4 —
407	Hf	Cl	2-(2-Fu)	4-Ph	2	2-(2-Fu)	4-Ph	2	—C 2 (Me) 4 —
408	Ti	Cl	2-(2-Fu)	4-Ph	2	2-(2-Fu)	4-Ph	2	—C 2 (Me) 4 —
409	Hf	Cl	2-(2-Fu)	3-Me, 7-Me	3	2-(2-Fu)	3-Me, 7-Me	3	—C 2 (Me) 4 —
410	Ti	Cl	2-(2-Fu)	3-Me, 7-Me	3	2-(2-Fu)	3-Me, 7-Me	3	—C 2 (Me) 4 —
411	Zr	Cl	2-(3-Fu)	4-Ph	2	2-(3-Fu)	4-Ph	2	—C 2 (Me) 4 —
412	Zr	Cl	2-(3-Fu)	4-Ph	2	2-(3-Fu)	4-Ph	2	—C 2 (Me) 4 —
413	Zr	Cl	2-[2-(3-Me—Fu)]	4-Ph	2	2-[2-(3-Me—Fu)]	4-Ph	2	—C 2 (Me) 4 —
414	Zr	Cl	2-[2-(3-Me—Fu)]	—	1	2-[2-(3-Me—Fu)]	—	1	—C 2 (Me) 4 —
415	Zr	Cl	2-(2-Thie)	4-Ph	2	2-(2-Thie)	4-Ph	2	—C 2 (Me) 4 —
416	Zr	Cl	2-(2-Thie)	—	1	2-(2-Thie)	—	1	—C 2 (Me) 4 —
417	Zr	Cl	2-(2-Py)	4-Ph	2	2-(2-Py)	4-Ph	2	—C 2 (Me) 4 —
418	Zr	Cl	2-(2-Py)	—	1	2-(2-Py)	—	1	—C 2 (Me) 4 —
419	Zr	Cl	2-(2-BzFu)	4-Ph	2	2-(2-BzFu)	4-Ph	2	—C 2 (Me) 4 —
420	Zr	Cl	2-(2-BzFu)	—	1	2-(2-BzFu)	—	1	—C 2 (Me) 4 —
421	Zr	Cl	2-[2-(1-Me—Pyr)]	4-Ph	2	2-[2-(1-Me—Pyr)]	4-Ph	2	—C 2 (Me) 4 —
422	Zr	Cl	2-[2-(1-Me—Pyr)]	—	1	2-[2-(1-Me—Pyr)]	—	1	—C 2 (Me) 4 —

	TABLE 12
	CA 1 : Indenyl	CA 2 : Indenyl
No.	M	X	Ra	R 1	p + m	Ra	R 1	q + n	Y
423	Zr	Cl	2-(2-Fu)	—	1	2-(2-Fu)	—	1	—SiH 2 —
424	Zr	Cl	2-(2-Fu)	—	1	2-(2-Fu)	—	1	—Si(Me) 2 —
425	Zr	Cl	2-(2-Fu)	7-Me	2	2-(2-Fu)	7-Me	2	—Si(Me) 2 —
426	Zr	Cl	2-(2-Fu)	4-Me	2	2-(2-Fu)	4-Me	2	—Si(Me) 2 —
427	Zr	Cl	2-(2-Fu)	3-Me	2	2-(2-Fu)	3-Me	2	—Si(Me) 2 —
428	Zr	Cl	2-(2-Fu)	3-Me, 7-Me	3	2-(2-Fu)	3-Me, 7-Me	3	—Si(Me) 2 —
429	Zr	Cl	2-(2-Fu)	4-Me, 7-Me	3	2-(2-Fu)	4-Me, 7-Me	3	—Si(Me) 2 —
430	Zr	Cl	2-(2-Fu)	4-Cl	2	2-(2-Fu)	4-Cl	2	—Si(Me) 2 —
431	Zr	Cl	2-(2-Fu)	4-Et	2	2-(2-Fu)	4-Et	2	—Si(Me) 2 —
432	Zr	Cl	2-(2-Fu)	4-i-Pr	2	2-(2-Fu)	4-i-Pr	2	—Si(Me) 2 —
433	Zr	Cl	2-(2-Fu)	4-t-Bu	2	2-(2-Fu)	4-t-Bu	2	—Si(Me) 2 —
434	Zr	Cl	2-(2-Fu)	4-Ph	2	2-(2-Fu)	4-Ph	2	—Si(Me) 2 —
435	Zr	Cl	2-(2-Fu)	4-Np	2	2-(2-Fu)	4-Np	2	—Si(Me) 2 —
436	Zr	Cl	2-(2-Fu)	4-OMe	2	2-(2-Fu)	4-OMe	2	—Si(Me) 2 —
437	Zr	Cl	2-(2-Fu)	4-OPh	2	2-(2-Fu)	4-OPh	2	—Si(Me) 2 —
438	Zr	Cl	2-(2-Fu)	4-Bzl	2	2-(2-Fu)	4-Bzl	2	—Si(Me) 2 —
439	Zr	Cl	2-(2-Fu)	4-Tol	2	2-(2-Fu)	4-Tol	2	—Si(Me) 2 —
440	Zr	Cl	2-(2-Fu)	4-OBzl	2	2-(2-Fu)	4-OBzl	2	—Si(Me) 2 —
441	Zr	Cl	2-(2-Fu)	4-TMS	2	2-(2-Fu)	4-TMS	2	—Si(Me) 2 —
442	Zr	Cl	2-(2-Fu)	4-(1-Pyr)	2	2-(2-Fu)	4-(1-Pyr)	2	—Si(Me) 2 —
443	Zr	Cl	2-(2-Fu)	4-(1-Indo)	2	2-(2-Fu)	4-(1-Indo)	2	—Si(Me) 2 —
444	Zr	Cl	2-(2-Fu), 4-(2-Fu)	—	2	2-(2-Fu), 4-(2-Fu)	—	2	—Si(Me) 2 —
445	Zr	Cl	2-(2-Fu), 4-(2-Thie)	—	2	2-(2-Fu), 4-(2-Thie)	—	2	—Si(Me) 2 —
446	Zr	Cl	2-(2-Fu), 4-(2-BzFu)	—	2	2-(2-Fu), 4-(2-BzFu)	—	2	—Si(Me) 2 —
447	Zr	Cl	2-(2-Fu), 4-(2-Py)	—	2	2-(2-Fu), 4-(2-Py)	—	2	—Si(Me) 2 —
448	Zr	Cl	2-(2-Fu), 4-(1-MePyr)	—	2	2-(2-Fu), 4-(1-MePyr)	—	2	—Si(Me) 2 —
449	Zr	Cl	2-(2-Fu)	4-Et, 7-Et	3	2-(2-Fu)	4-Et, 7-Et	3	—Si(Me) 2 —
450	Zr	Cl	2-(2-Fu)	4-i-Pr, 7-i-Pr	3	2-(2-Fu)	4-i-Pr, 7-i-Pr	3	—Si(Me) 2 —
451	Zr	Cl	2-(2-Fu)	4-t-Bu, 7-t-Bu	3	2-(2-Fu)	4-t-Bu, 7-t-Bu	3	—Si(Me) 2 —
452	Zr	Cl	2-(2-Fu)	4-Ph, 7-Ph	3	2-(2-Fu)	4-Ph, 7-Ph	3	—Si(Me) 2 —
453	Zr	Cl	2-(2-Fu)	3-Ph, 7-Me	3	2-(2-Fu)	3-Ph, 7-Me	3	—Si(Me) 2 —
454	Zr	Cl	2-(2-Fu)	4-Me, 7-Me	3	2-(2-Fu)	4-Me, 7-Me	3	—Si(Et) 2 —
455	Zr	Cl	2-(2-Fu)	4-Me, 7-Me	3	2-(2-Fu)	4-Me, 7-Me	3	—Si(Ph) 2 —
456	Zr	Me	2-(2-Fu)	4-Ph	2	2-(2-Fu)	4-Ph	2	—Si(Me) 2 —
457	Zr	Bzl	2-(2-Fu)	4-Ph	2	2-(2-Fu)	4-Ph	2	—Si(Me) 2 —
458	Hf	Cl	2-(2-Fu)	4-Ph	2	2-(2-Fu)	4-Ph	2	—Si(Me) 2 —
459	Ti	Cl	2-(2-Fu)	4-Ph	2	2-(2-Fu)	4-Ph	2	—Si(Me) 2 —
460	Hf	Cl	2-(2-Fu)	3-Me, 7-Me	3	2-(2-Fu)	3-Me, 7-Me	3	—Si(Me) 2 —
461	Ti	Cl	2-(2-Fu)	3-Me, 7-Me	3	2-(2-Fu)	3-Me, 7-Me	3	—Si(Me) 2 —
462	Zr	Cl	2-(3-Fu)	4-Ph	2	2-(3-Fu)	4-Ph	2	—Si(Me) 2 —
463	Zr	Cl	2-(3-Fu)	4-Ph	2	2-(3-Fu)	4-Ph	2	—Si(Me) 2 —
464	Zr	Cl	2-[2-(3-Me—Fu)]	4-Ph	2	2-[2-(3-Me—Fu)]	4-Ph	2	—Si(Me) 2 —
465	Zr	Cl	2-[2-(3-Me—Fu)]	—	1	2-[2-(3-Me—Fu)]	—	1	—Si(Me) 2 —
466	Zr	Cl	2-(2-Thie)	4-Ph	2	2-(2-Thie)	4-Ph	2	—Si(Me) 2 —
467	Zr	Cl	2-(2-Thie)	—	1	2-(2-Thie)	—	1	—Si(Me) 2 —
468	Zr	Cl	2-(2-Py)	4-Ph	2	2-(2-Py)	4-Ph	2	—Si(Me) 2 —
469	Zr	Cl	2-(2-Py)	—	1	2-(2-Py)	—	1	—Si(Me) 2 —
470	Zr	Cl	2-(2-BzFu)	4-Ph	2	2-(2-BzFu)	4-Ph	2	—Si(Me) 2 —
471	Zr	Cl	2-(2-BzFu)	—	1	2-(2-BzFu)	—	1	—Si(Me) 2 —
472	Zr	Cl	2-[2-(1-Me—Pyr)]	4-Ph	2	2-[2-(1-Me—Pyr)]	4-Ph	2	—Si(Me) 2 —
473	Zr	Cl	2-[2-(1-Me—Pyr)]	—	1	2-[2-(1-Me—Pyr)]	—	1	—Si(Me) 2 —

	TABLE 13
	CA 1 : Indenyl	CA 2 : Indenyl
No.	M	X	Ra 1	R 1	p + m	Ra 2	R 1	q + n	Y
474	Zr	Cl	2-(2-Fu)	—	1	2-(2-Fu)	—	1	—GeH 2 —
475	Zr	Cl	2-(2-Fu)	—	1	2-(2-Fu)	—	1	—Ge(Me) 2 —
476	Zr	Cl	2-(2-Fu)	7-Me	2	2-(2-Fu)	7-Me	2	—Ge(Me) 2 —
477	Zr	Cl	2-(2-Fu)	4-Me	2	2-(2-Fu)	4-Me	2	—Ge(Me) 2 —
478	Zr	Cl	2-(2-Fu)	3-Me	2	2-(2-Fu)	3-Me	2	—Ge(Me) 2 —
479	Zr	Cl	2-(2-Fu)	3-Me, 7-Me	3	2-(2-Fu)	3-Me, 7-Me	3	—Ge(Me) 2 —
480	Zr	Cl	2-(2-Fu)	4-Me, 7-Me	3	2-(2-Fu)	4-Me, 7-Me	3	—Ge(Me) 2 —
481	Zr	Cl	2-(2-Fu)	4-Cl	2	2-(2-Fu)	4-Cl	2	—Ge(Me) 2 —
482	Zr	Cl	2-(2-Fu)	4-Et	2	2-(2-Fu)	4-Et	2	—Ge(Me) 2 —
483	Zr	Cl	2-(2-Fu)	4-i-Pr	2	2-(2-Fu)	4-i-Pr	2	—Ge(Me) 2 —
484	Zr	Cl	2-(2-Fu)	4-t-Bu	2	2-(2-Fu)	4-t-Bu	2	—Ge(Me) 2 —
485	Zr	Cl	2-(2-Fu)	4-Ph	2	2-(2-Fu)	4-Ph	2	—Ge(Me) 2 —
486	Zr	Cl	2-(2-Fu)	4-Np	2	2-(2-Fu)	4-Np	2	—Ge(Me) 2 —
487	Zr	Cl	2-(2-Fu)	4-OMe	2	2-(2-Fu)	4-OMe	2	—Ge(Me) 2 —
488	Zr	Cl	2-(2-Fu)	4-OPh	2	2-(2-Fu)	4-OPh	2	—Ge(Me) 2 —
489	Zr	Cl	2-(2-Fu)	4-Bzl	2	2-(2-Fu)	4-Bzl	2	—Ge(Me) 2 —
490	Zr	Cl	2-(2-Fu)	4-Tol	2	2-(2-Fu)	4-Tol	2	—Ge(Me) 2 —
491	Zr	Cl	2-(2-Fu)	4-OBzl	2	2-(2-Fu)	4-OBzl	2	—Ge(Me) 2 —
492	Zr	Cl	2-(2-Fu)	4-TMS	2	2-(2-Fu)	4-TMS	2	—Ge(Me) 2 —
493	Zr	Cl	2-(2-Fu)	4-(1-Pyr)	2	2-(2-Fu)	4-(1-Pyr)	2	—Ge(Me) 2 —
494	Zr	Cl	2-(2-Fu)	4-(1-Indo)	2	2-(2-Fu)	4-(1-Indo)	2	—Ge(Me) 2 —
495	Zr	Cl	2-(2-Fu), 4-(2-Fu)	—	2	2-(2-Fu), 4-(2-Fu)	—	2	—Ge(Me) 2 —
496	Zr	Cl	2-(2-Fu), 4-(2-Thie)	—	2	2-(2-Fu), 4-(2-Thie)	—	2	—Ge(Me) 2 —
497	Zr	Cl	2-(2-Fu), 4-(2-BzFu)	—	2	2-(2-Fu), 4-(2-BzFu)	—	2	—Ge(Me) 2 —
498	Zr	Cl	2-(2-Fu), 4-(2-Py)	—	2	2-(2-Fu), 4-(2-Py)	—	2	—Ge(Me) 2 —
499	Zr	Cl	2-(2-Fu), 4-(1-MePyr)	—	2	2-(2-Fu), 4-(1-MePyr)	—	2	—Ge(Me) 2 —
500	Zr	Cl	2-(2-Fu)	4-Et, 7-Et	3	2-(2-Fu)	4-Et, 7-Et	3	—Ge(Me) 2 —
501	Zr	Cl	2-(2-Fu)	4-i-Pr, 7-i-Pr	3	2-(2-Fu)	4-i-Pr, 7-i-Pr	3	—Ge(Me) 2 —
502	Zr	Cl	2-(2-Fu)	4-t-Bu, 7-t-Bu	3	2-(2-Fu)	4-t-Bu, 7-t-Bu	3	—Ge(Me) 2 —
503	Zr	Cl	2-(2-Fu)	4-Ph, 7-Ph	3	2-(2-Fu)	4-Ph, 7-Ph	3	—Ge(Me) 2 —
504	Zr	Cl	2-(2-Fu)	3-Ph, 7-Me	3	2-(2-Fu)	3-Ph, 7-Me	3	—Ge(Me) 2 —
505	Zr	Cl	2-(2-Fu)	4-Me, 7-Me	3	2-(2-Fu)	4-Me, 7-Me	3	—Ge(Et) 2 —
506	Zr	Cl	2-(2-Fu)	4-Me, 7-Me	3	2-(2-Fu)	4-Me, 7-Me	3	—Ge(Ph) 2 —
507	Zr	Me	2-(2-Fu)	4-Ph	2	2-(2-Fu)	4-Ph	2	—Ge(Me) 2 —
508	Zr	Bzl	2-(2-Fu)	4-Ph	2	2-(2-Fu)	4-Ph	2	—Ge(Me) 2 —
509	Hf	Cl	2-(2-Fu)	4-Ph	2	2-(2-Fu)	4-Ph	2	—Ge(Me) 2 —
510	Ti	Cl	2-(2-Fu)	4-Ph	2	2-(2-Fu)	4-Ph	2	—Ge(Me) 2 —
511	Hf	Cl	2-(2-Fu)	3-Me, 7-Me	3	2-(2-Fu)	3-Me, 7-Me	3	—Ge(Me) 2 —
512	Ti	Cl	2-(2-Fu)	3-Me, 7-Me	3	2-(2-Fu)	3-Me, 7-Me	3	—Ge(Me) 2 —
513	Zr	Cl	2-(3-Fu)	4-Ph	2	2-(3-Fu)	4-Ph	2	—Ge(Me) 2 —
514	Zr	Cl	2-(3-Fu)	4-Ph	2	2-(3-Fu)	4-Ph	2	—Ge(Me) 2 —
515	Zr	Cl	2-[2-(3-Me—Fu)]	4-Ph	2	2-[2-(3-Me—Fu)]	4-Ph	2	—Ge(Me) 2 —
516	Zr	Cl	2-[2-(3-Me—Fu)]	—	1	2-[2-(3-Me—Fu)]	—	1	—Ge(Me) 2 —
517	Zr	Cl	2-(2-Thie)	4-Ph	2	2-(2-Thie)	4-Ph	2	—Ge(Me) 2 —
518	Zr	Cl	2-(2-Thie)	—	1	2-(2-Thie)	—	1	—Ge(Me) 2 —
519	Zr	Cl	2-(2-Py)	4-Ph	2	2-(2-Py)	4-Ph	2	—Ge(Me) 2 —
520	Zr	Cl	2-(2-Py)	—	1	2-(2-Py)	—	1	—Ge(Me) 2 —
521	Zr	Cl	2-(2-BzFu)	4-Ph	2	2-(2-BzFu)	4-Ph	2	—Ge(Me) 2 —
522	Zr	Cl	2-(2-BzFu)	—	1	2-(2-BzFu)	—	1	—Ge(Me) 2 —
523	Zr	Cl	2-[2-(1-Me—Pyr)]	4-Ph	2	2-[2-(1-Me—Pyr)]	4-Ph	2	—Ge(Me) 2 —
524	Zr	Cl	2-[2-(1-Me—Pyr)]	—	1	2-[2-(1-Me—Pyr)]	—	1	—Ge(Me) 2 —

	TABLE 14
	CA 1 : Tetrahydroindenyl	CA 2 : Tetrahydroindenyl
No.	M	X	Ra	R 1	p + m	Ra	R 1	q + n	Y
525	Zr	Cl	2-(2-Fu)	—	1	2-(2-Fu)	—	1	—CH 2 —
526	Zr	Cl	2-(2-Fu)	—	1	2-(2-Fu)	—	1	—C(Me) 2 —
527	Zr	Cl	2-(2-Fu)	7-Me	2	2-(2-Fu)	7-Me	2	—C(Me) 2 —
528	Zr	Cl	2-(2-Fu)	4-Me	2	2-(2-Fu)	4-Me	2	—C(Me) 2 —
529	Zr	Cl	2-(2-Fu)	3-Me	2	2-(2-Fu)	3-Me	2	—C(Me) 2 —
530	Zr	Cl	2-(2-Fu)	3-Me, 7-Me	3	2-(2-Fu)	3-Me, 7-Me	3	—C(Me) 2 —
531	Zr	Cl	2-(2-Fu)	4-Me, 7-Me	3	2-(2-Fu)	4-Me, 7-Me	3	—C(Me) 2 —
532	Zr	Cl	2-(2-Fu)	4-Cl	2	2-(2-Fu)	4-Cl	2	—C(Me) 2 —
533	Zr	Cl	2-(2-Fu)	4-Et	2	2-(2-Fu)	4-Et	2	—C(Me) 2 —
534	Zr	Cl	2-(2-Fu)	4-i-Pr	2	2-(2-Fu)	4-i-Pr	2	—C(Me) 2 —
535	Zr	Cl	2-(2-Fu)	4-t-Bu	2	2-(2-Fu)	4-t-Bu	2	—C(Me) 2 —
536	Zr	Cl	2-(2-Fu)	4-Ph	2	2-(2-Fu)	4-Ph	2	—C(Me) 2 —
537	Zr	Cl	2-(2-Fu)	4-Np	2	2-(2-Fu)	4-Np	2	—C(Me) 2 —
538	Zr	Cl	2-(2-Fu)	4-OMe	2	2-(2-Fu)	4-OMe	2	—C(Me) 2 —
539	Zr	Cl	2-(2-Fu)	4-OPh	2	2-(2-Fu)	4-OPh	2	—C(Me) 2 —
540	Zr	Cl	2-(2-Fu)	4-Bzl	2	2-(2-Fu)	4-Bzl	2	—C(Me) 2 —
541	Zr	Cl	2-(2-Fu)	4-Tol	2	2-(2-Fu)	4-Tol	2	—C(Me) 2 —
542	Zr	Cl	2-(2-Fu)	4-OBzl	2	2-(2-Fu)	4-OBzl	2	—C(Me) 2 —
543	Zr	Cl	2-(2-Fu)	4-TMS	2	2-(2-Fu)	4-TMS	2	—C(Me) 2 —
544	Zr	Cl	2-(2-Fu)	4-(1-Pyr)	2	2-(2-Fu)	4-(1-Pyr)	2	—C(Me) 2 —
545	Zr	Cl	2-(2-Fu)	4-(1-Indo)	2	2-(2-Fu)	4-(1-Indo)	2	—C(Me) 2 —
546	Zr	Cl	2-(2-Fu), 4-(2-Fu)	—	2	2-(2-Fu), 4-(2-Fu)	—	2	—C(Me) 2 —
547	Zr	Cl	2-(2-Fu), 4-(2-Thie)	—	2	2-(2-Fu), 4-(2-Thie)	—	2	—C(Me) 2 —
548	Zr	Cl	2-(2-Fu), 4-(2-BzFu)	—	2	2-(2-Fu), 4-(2-BzFu)	—	2	—C(Me) 2 —
549	Zr	Cl	2-(2-Fu), 4-(2-Py)	—	2	2-(2-Fu), 4-(2-Py)	—	2	—C(Me) 2 —
550	Zr	Cl	2-(2-Fu), 4-(1-MePyr)	—	2	2-(2-Fu), 4-(1-MePyr)	—	2	—C(Me) 2 —
551	Zr	Cl	2-(2-Fu)	4-Et, 7-Et	3	2-(2-Fu)	4-Et, 7-Et	3	—C(Me) 2 —
552	Zr	Cl	2-(2-Fu)	4-i-Pr, 7-i-Pr	3	2-(2-Fu)	4-i-Pr, 7-i-Pr	3	—C(Me) 2 —
553	Zr	Cl	2-(2-Fu)	4-t-Bu, 7-t-Bu	3	2-(2-Fu)	4-t-Bu, 7-t-Bu	3	—C(Me) 2 —
554	Zr	Cl	2-(2-Fu)	4-Ph, 7-Ph	3	2-(2-Fu)	4-Ph, 7-Ph	3	—C(Me) 2 —
555	Zr	Cl	2-(2-Fu)	3-Ph, 7-Me	3	2-(2-Fu)	3-Ph, 7-Me	3	—C(Me) 2 —
556	Zr	Cl	2-(2-Fu)	4-Me, 7-Me	3	2-(2-Fu)	4-Me, 7-Me	3	—C(Et) 2 —
557	Zr	Cl	2-(2-Fu)	4-Me, 7-Me	3	2-(2-Fu)	4-Me, 7-Me	3	—C(Ph) 2 —
558	Zr	Me	2-(2-Fu)	4-Ph	2	2-(2-Fu)	4-Ph	2	—C(Me) 2 —
559	Zr	Bzl	2-(2-Fu)	4-Ph	2	2-(2-Fu)	4-Ph	2	—C(Me) 2 —
560	Hf	Cl	2-(2-Fu)	4-Ph	2	2-(2-Fu)	4-Ph	2	—C(Me) 2 —
561	Ti	Cl	2-(2-Fu)	4-Ph	2	2-(2-Fu)	4-Ph	2	—C(Me) 2 —
562	Hf	Cl	2-(2-Fu)	3-Me, 7-Me	3	2-(2-Fu)	3-Me, 7-Me	3	—C(Me) 2 —
563	Ti	Cl	2-(2-Fu)	3-Me, 7-Me	3	2-(2-Fu)	3-Me, 7-Me	3	—C(Me) 2 —
564	Zr	Cl	2-(3-Fu)	4-Ph	2	2-(3-Fu)	4-Ph	2	—C(Me) 2 —
565	Zr	Cl	2-(3-Fu)	4-Ph	2	2-(3-Fu)	4-Ph	2	—C(Me) 2 —
566	Zr	Cl	2-[2-(3-Me—Fu)]	4-Ph	2	2-[2-(3-Me—Fu)]	4-Ph	2	—C(Me) 2 —
567	Zr	Cl	2-[2-(3-Me—Fu)]	—	1	2-[2-(3-Me—Fu)]	—	1	—C(Me) 2 —
568	Zr	Cl	2-(2-Thie)	4-Ph	2	2-(2-Thie)	4-Ph	2	—C(Me) 2 —
569	Zr	Cl	2-(2-Thie)	—	1	2-(2-Thie)	—	1	—C(Me) 2 —
570	Zr	Cl	2-(2-Py)	4-Ph	2	2-(2-Py)	4-Ph	2	—C(Me) 2 —
571	Zr	Cl	2-(2-Py)	—	1	2-(2-Py)	—	1	—C(Me) 2 —
572	Zr	Cl	2-(2-BzFu)	4-Ph	2	2-(2-BzFu)	4-Ph	2	—C(Me) 2 —
573	Zr	Cl	2-(2-BzFu)	—	1	2-(2-BzFu)	—	1	—C(Me) 2 —
574	Zr	Cl	2-[2-(1-Me—Pyr)]	4-Ph	2	2-[2-(1-Me—Pyr)]	4-Ph	2	—C(Me) 2 —
575	Zr	Cl	2-[2-(1-Me—Pyr)]	—	1	2-[2-(1-Me—Pyr)]	—	1	—C(Me) 2 —

	TABLE 15
	CA 1 : Tetrahydroindenyl	CA 2 : Tetrahydroindenyl
No.	M	X	Ra	R 1	p + m	Ra	R 1	q + n	Y
576	Zr	Cl	2-(2-Fu)	—	1	2-(2-Fu)	—	1	—CH 2 CH 2 —
577	Zr	Cl	2-(2-Fu)	—	1	2-(2-Fu)	—	1	—C 2 (Me) 4 —
578	Zr	Cl	2-(2-Fu)	7-Me	2	2-(2-Fu)	7-Me	2	—C 2 (Me) 4 —
579	Zr	Cl	2-(2-Fu)	4-Me	2	2-(2-Fu)	4-Me	2	—C 2 (Me) 4 —
580	Zr	Cl	2-(2-Fu)	3-Me	2	2-(2-Fu)	3-Me	2	—C 2 (Me) 4 —
581	Zr	Cl	2-(2-Fu)	3-Me, 7-Me	3	2-(2-Fu)	3-Me, 7-Me	3	—C 2 (Me) 4 —
582	Zr	Cl	2-(2-Fu)	4-Me, 7-Me	3	2-(2-Fu)	4-Me, 7-Me	3	—C 2 (Me) 4 —
583	Zr	Cl	2-(2-Fu)	4-Cl	2	2-(2-Fu)	4-Cl	2	—C 2 (Me) 4 —
584	Zr	Cl	2-(2-Fu)	4-Et	2	2-(2-Fu)	4-Et	2	—C 2 (Me) 4 —
585	Zr	Cl	2-(2-Fu)	4-I—Pr	2	2-(2-Fu)	4-I—Pr	2	—C 2 (Me) 4 —
586	Zr	Cl	2-(2-Fu)	4-t-Bu	2	2-(2-Fu)	4-t-Bu	2	—C 2 (Me) 4 —
587	Zr	Cl	2-(2-Fu)	4-Ph	2	2-(2-Fu)	4-Ph	2	—C 2 (Me) 4 —
588	Zr	Cl	2-(2-Fu)	4-Np	2	2-(2-Fu)	4-Np	2	—C 2 (Me) 4 —
589	Zr	Cl	2-(2-Fu)	4-OMe	2	2-(2-Fu)	4-OMe	2	—C 2 (Me) 4 —
590	Zr	Cl	2-(2-Fu)	4-OPh	2	2-(2-Fu)	4-OPh	2	—C 2 (Me) 4 —
591	Zr	Cl	2-(2-Fu)	4-Bzl	2	2-(2-Fu)	4-Bzl	2	—C 2 (Me) 4 —
592	Zr	Cl	2-(2-Fu)	4-Tol	2	2-(2-Fu)	4-Tol	2	—C 2 (Me) 4 —
593	Zr	Cl	2-(2-Fu)	4-OBzl	2	2-(2-Fu)	4-OBzl	2	—C 2 (Me) 4 —
594	Zr	Cl	2-(2-Fu)	4-TMS	2	2-(2-Fu)	4-TMS	2	—C 2 (Me) 4 —
595	Zr	Cl	2-(2-Fu)	4-(1-Pyr)	2	2-(2-Fu)	4-(1-Pyr)	2	—C 2 (Me) 4 —
596	Zr	Cl	2-(2-Fu)	4-(1-Indo)	2	2-(2-Fu)	4-(1-Indo)	2	—C 2 (Me) 4 —
597	Zr	Cl	2-(2-Fu), 4-(2-Fu)	—	2	2-(2-Fu), 4-(2-Fu)	—	2	—C 2 (Me) 4 —
598	Zr	Cl	2-(2-Fu), 4-(2-Thie)	—	2	2-(2-Fu), 4-(2-Thie)	—	2	—C 2 (Me) 4 —
599	Zr	Cl	2-(2-Fu), 4-(2-BzFu)	—	2	2-(2-Fu), 4-(2-BzFu)	—	2	—C 2 (Me) 4 —
600	Zr	Cl	2-(2-Fu), 4-(2-Py)	—	2	2-(2-Fu), 4-(2-Py)	—	2	—C 2 (Me) 4 —
601	Zr	Cl	2-(2-Fu), 4-(1-MePyr)	—	2	2-(2-Fu), 4-(1-MePyr)	—	2	—C 2 (Me) 4 —
602	Zr	Cl	2-(2-Fu)	4-Et, 7-Et	3	2-(2-Fu)	4-Et, 7-Et	3	—C 2 (Me) 4 —
603	Zr	Cl	2-(2-Fu)	4-I—Pr, 7-I—Pr	3	2-(2-Fu)	4-I—Pr, 7-I—Pr	3	—C 2 (Me) 4 —
604	Zr	Cl	2-(2-Fu)	4-t-Bu, 7-t-Bu	3	2-(2-Fu)	4-t-Bu, 7-t-Bu	3	—C 2 (Me) 4 —
605	Zr	Cl	2-(2-Fu)	4-Ph, 7-Ph	3	2-(2-Fu)	4-Ph, 7-Ph	3	—C 2 (Me) 4 —
606	Zr	Cl	2-(2-Fu)	3-Ph, 7-Me	3	2-(2-Fu)	3-Ph, 7-Me	3	—C 2 (Me) 4 —
607	Zr	Cl	2-(2-Fu)	4-Me, 7-Me	3	2-(2-Fu)	4-Me, 7-Me	3	—C 2 (Et) 4 —
608	Zr	Cl	2-(2-Fu)	4-Me, 7-Me	3	2-(2-Fu)	4-Me, 7-Me	3	—C 2 (Ph) 4 —
609	Zr	Me	2-(2-Fu)	4-Ph	2	2-(2-Fu)	4-Ph	2	—C 2 (Me) 4 —
610	Zr	Bzl	2-(2-Fu)	4-Ph	2	2-(2-Fu)	4-Ph	2	—C 2 (Me) 4 —
611	Hf	Cl	2-(2-Fu)	4-Ph	2	2-(2-Fu)	4-Ph	2	—C 2 (Me) 4 —
612	Ti	Cl	2-(2-Fu)	4-Ph	2	2-(2-Fu)	4-Ph	2	—C 2 (Me) 4 —
613	Hf	Cl	2-(2-Fu)	3-Me, 7-Me	3	2-(2-Fu)	3-Me, 7-Me	3	—C 2 (Me) 4 —
614	Ti	Cl	2-(2-Fu)	3-Me, 7-Me	3	2-(2-Fu)	3-Me, 7-Me	3	—C 2 (Me) 4 —
615	Zr	Cl	2-(3-Fu)	4-Ph	2	2-(3-Fu)	4-Ph	2	—C 2 (Me) 4 —
616	Zr	Cl	2-(3-Fu)	4-Ph	2	2-(3-Fu)	4-Ph	2	—C 2 (Me) 4 —
617	Zr	Cl	2-[2-(3-Me—Fu)]	4-Ph	2	2-[2-(3-Me—Fu)]	4-Ph	2	—C 2 (Me) 4 —
618	Zr	Cl	2-[2-(3-Me—Fu)]	—	1	2-[2-(3-Me—Fu)]	—	1	—C 2 (Me) 4 —
619	Zr	Cl	2-(2-Thie)	4-Ph	2	2-(2-Thie)	4-Ph	2	—C 2 (Me) 4 —
620	Zr	Cl	2-(2-Thie)	—	1	2-(2-Thie)	—	1	—C 2 (Me) 4 —
621	Zr	Cl	2-(2-Py)	4-Ph	2	2-(2-Py)	4-Ph	2	—C 2 (Me) 4 —
622	Zr	Cl	2-(2-Py)	—	1	2-(2-Py)	—	1	—C 2 (Me) 4 —
623	Zr	Cl	2-(2-BzFu)	4-Ph	2	2-(2-BzFu)	4-Ph	2	—C 2 (Me) 4 —
624	Zr	Cl	2-(2-BzFu)	—	1	2-(2-BzFu)	—	1	—C 2 (Me) 4 —
625	Zr	Cl	2-[2-(N—Me—Pyr)]	4-Ph	2	2-[2-(N—Me—Pyr)]	4-Ph	2	—C 2 (Me) 4 —
626	Zr	Cl	2-[2-(N—Me—Pyr)]	—	1	2-[2-(N—Me—Pyr)]	—	1	—C 2 (Me) 4 —

	TABLE 16
	CA 1 : Tetrahydroindenyl	CA 2 : Tetrahydroindenyl
No.	M	X	Ra	R 1	p + m	Ra	R 1	q + n	Y
627	Zr	Cl	2-(2-Fu)	—	1	2-(2-Fu)	—	1	—SiH 2 —
628	Zr	Cl	2-(2-Fu)	—	1	2-(2-Fu)	—	1	—Si(Me) 2 —
629	Zr	Cl	2-(2-Fu)	7-Me	2	2-(2-Fu)	7-Me	2	—Si(Me) 2 —
630	Zr	Cl	2-(2-Fu)	4-Me	2	2-(2-Fu)	4-Me	2	—Si(Me) 2 —
631	Zr	Cl	2-(2-Fu)	3-Me	2	2-(2-Fu)	3-Me	2	—Si(Me) 2 —
632	Zr	Cl	2-(2-Fu)	3-Me, 7-Me	3	2-(2-Fu)	3-Me, 7-Me	3	—Si(Me) 2 —
633	Zr	Cl	2-(2-Fu)	4-Me, 7-Me	3	2-(2-Fu)	4-Me, 7-Me	3	—Si(Me) 2 —
634	Zr	Cl	2-(2-Fu)	4-Cl	2	2-(2-Fu)	4-Cl	2	—Si(Me) 2 —
635	Zr	Cl	2-(2-Fu)	4-Et	2	2-(2-Fu)	4-Et	2	—Si(Me) 2 —
636	Zr	Cl	2-(2-Fu)	4-I—Pr	2	2-(2-Fu)	4-I—Pr	2	—Si(Me) 2 —
637	Zr	Cl	2-(2-Fu)	4-t-Bu	2	2-(2-Fu)	4-t-Bu	2	—Si(Me) 2 —
638	Zr	Cl	2-(2-Fu)	4-Ph	2	2-(2-Fu)	4-Ph	2	—Si(Me) 2 —
639	Zr	Cl	2-(2-Fu)	4-Np	2	2-(2-Fu)	4-Np	2	—Si(Me) 2 —
640	Zr	Cl	2-(2-Fu)	4-OMe	2	2-(2-Fu)	4-OMe	2	—Si(Me) 2 —
641	Zr	Cl	2-(2-Fu)	4-OPh	2	2-(2-Fu)	4-OPh	2	—Si(Me) 2 —
642	Zr	Cl	2-(2-Fu)	4-Bzl	2	2-(2-Fu)	4-Bzl	2	—Si(Me) 2 —
643	Zr	Cl	2-(2-Fu)	4-Tol	2	2-(2-Fu)	4-Tol	2	—Si(Me) 2 —
644	Zr	Cl	2-(2-Fu)	4-OBzl	2	2-(2-Fu)	4-OBzl	2	—Si(Me) 2 —
645	Zr	Cl	2-(2-Fu)	4-TMS	2	2-(2-Fu)	4-TMS	2	—Si(Me) 2 —
646	Zr	Cl	2-(2-Fu)	4-(1-Pyr)	2	2-(2-Fu)	4-(1-Pyr)	2	—Si(Me) 2 —
647	Zr	Cl	2-(2-Fu)	4-(1-Indo)	2	2-(2-Fu)	4-(1-Indo)	2	—Si(Me) 2 —
648	Zr	Cl	2-(2-Fu), 4-(2-Fu)	—	2	2-(2-Fu), 4-(2-Fu)	—	2	—Si(Me) 2 —
649	Zr	Cl	2-(2-Fu), 4-(2-Thie)	—	2	2-(2-Fu), 4-(2-Thie)	—	2	—Si(Me) 2 —
650	Zr	Cl	2-(2-Fu), 4-(2-BzFu)	—	2	2-(2-Fu), 4-(2-BzFu)	—	2	—Si(Me) 2 —
651	Zr	Cl	2-(2-Fu), 4-(2-Py)	—	2	2-(2-Fu), 4-(2-Py)	—	2	—Si(Me) 2 —
652	Zr	Cl	2-(2-Fu), 4-(1-MePyr)	—	2	2-(2-Fu), 4-(1-MePyr)	—	2	—Si(Me) 2 —
653	Zr	Cl	2-(2-Fu)	4-Et, 7-Et	3	2-(2-Fu)	4-Et, 7-Et	3	—Si(Me) 2 —
654	Zr	Cl	2-(2-Fu)	4-I—Pr, 7-I—Pr	3	2-(2-Fu)	4-I—Pr, 7-I—Pr	3	—Si(Me) 2 —
655	Zr	Cl	2-(2-Fu)	4-t-Bu, 7-t-Bu	3	2-(2-Fu)	4-t-Bu, 7-t-Bu	3	—Si(Me) 2 —
656	Zr	Cl	2-(2-Fu)	4-Ph, 7-Ph	3	2-(2-Fu)	4-Ph, 7-Ph	3	—Si(Me) 2 —
657	Zr	Cl	2-(2-Fu)	3-Ph, 7-Me	3	2-(2-Fu)	3-Ph, 7-Me	3	—Si(Me) 2 —
658	Zr	Cl	2-(2-Fu)	4-Me, 7-Me	3	2-(2-Fu)	4-Me, 7-Me	3	—Si(Et) 2 —
659	Zr	Cl	2-(2-Fu)	4-Me, 7-Me	3	2-(2-Fu)	4-Me, 7-Me	3	—Si(Ph) 2 —
660	Zr	Me	2-(2-Fu)	4-Ph	2	2-(2-Fu)	4-Ph	2	—Si(Me) 2 —
661	Zr	Bzl	2-(2-Fu)	4-Ph	2	2-(2-Fu)	4-Ph	2	—Si(Me) 2 —
662	Hf	Cl	2-(2-Fu)	4-Ph	2	2-(2-Fu)	4-Ph	2	—Si(Me) 2 —
663	Ti	Cl	2-(2-Fu)	4-Ph	2	2-(2-Fu)	4-Ph	2	—Si(Me) 2 —
664	Hf	Cl	2-(2-Fu)	3-Me, 7-Me	3	2-(2-Fu)	3-Me, 7-Me	3	—Si(Me) 2 —
665	Ti	Cl	2-(2-Fu)	3-Me, 7-Me	3	2-(2-Fu)	3-Me, 7-Me	3	—Si(Me) 2 —
666	Zr	Cl	2-(3-Fu)	4-Ph	2	2-(3-Fu)	4-Ph	2	—Si(Me) 2 —
667	Zr	Cl	2-(3-Fu)	4-Ph	2	2-(3-Fu)	4-Ph	2	—Si(Me) 2 —
668	Zr	Cl	2-[2-(3-Me—Fu)]	4-Ph	2	2-[2-(3-Me—Fu)]	4-Ph	2	—Si(Me) 2 —
669	Zr	Cl	2-[2-(3-Me—Fu)]	—	1	2-[2-(3-Me—Fu)]	—	1	—Si(Me) 2 —
670	Zr	Cl	2-(2-Thie)	4-Ph	2	2-(2-Thie)	4-Ph	2	—Si(Me) 2 —
671	Zr	Cl	2-(2-Thie)	—	1	2-(2-Thie)	—	1	—Si(Me) 2 —
672	Zr	Cl	2-(2-Py)	4-Ph	2	2-(2-Py)	4-Ph	2	—Si(Me) 2 —
673	Zr	Cl	2-(2-Py)	—	1	2-(2-Py)	—	1	—Si(Me) 2 —
674	Zr	Cl	2-(2-BzFu)	4-Ph	2	2-(2-BzFu)	4-Ph	2	—Si(Me) 2 —
675	Zr	Cl	2-(2-BzFu)	—	1	2-(2-BzFu)	—	1	—Si(Me) 2 —
676	Zr	Cl	2-[2-(N—Me—Pyr)]	4-Ph	2	2-[2-(N—Me—Pyr)]	4-Ph	2	—Si(Me) 2 —
677	Zr	Cl	2-[2-(N—Me—Pyr)]	—	1	2-[2-(N—Me—Pyr)]	—	1	—Si(Me) 2 —

	TABLE 17
	CA 1 : Tetrahydroindenyl	CA 2 : Tetrahydroindenyl
No.	M	X	Ra	R 1	p + m	Ra	R 1	q + n	Y
678	Zr	Cl	2-(2-Fu)	—	1	2-(2-Fu)	—	1	—GeH 2 —
679	Zr	Cl	2-(2-Fu)	—	1	2-(2-Fu)	—	1	—Ge(Me) 2 —
680	Zr	Cl	2-(2-Fu)	7-Me	2	2-(2-Fu)	7-Me	2	—Ge(Me) 2 —
681	Zr	Cl	2-(2-Fu)	4-Me	2	2-(2-Fu)	4-Me	2	—Ge(Me) 2 —
682	Zr	Cl	2-(2-Fu)	3-Me	2	2-(2-Fu)	3-Me	2	—Ge(Me) 2 —
683	Zr	Cl	2-(2-Fu)	3-Me, 7-Me	3	2-(2-Fu)	3-Me, 7-Me	3	—Ge(Me) 2 —
684	Zr	Cl	2-(2-Fu)	4-Me, 7-Me	3	2-(2-Fu)	4-Me, 7-Me	3	—Ge(Me) 2 —
685	Zr	Cl	2-(2-Fu)	4-Cl	2	2-(2-Fu)	4-Cl	2	—Ge(Me) 2 —
686	Zr	Cl	2-(2-Fu)	4-Et	2	2-(2-Fu)	4-Et	2	—Ge(Me) 2 —
687	Zr	Cl	2-(2-Fu)	4-I—Pr	2	2-(2-Fu)	4-I—Pr	2	—Ge(Me) 2 —
688	Zr	Cl	2-(2-Fu)	4-t-Bu	2	2-(2-Fu)	4-t-Bu	2	—Ge(Me) 2 —
689	Zr	Cl	2-(2-Fu)	4-Ph	2	2-(2-Fu)	4-Ph	2	—Ge(Me) 2 —
690	Zr	Cl	2-(2-Fu)	4-Np	2	2-(2-Fu)	4-Np	2	—Ge(Me) 2 —
691	Zr	Cl	2-(2-Fu)	4-OMe	2	2-(2-Fu)	4-OMe	2	—Ge(Me) 2 —
692	Zr	Cl	2-(2-Fu)	4-OPh	2	2-(2-Fu)	4-OPh	2	—Ge(Me) 2 —
693	Zr	Cl	2-(2-Fu)	4-Bzl	2	2-(2-Fu)	4-Bzl	2	—Ge(Me) 2 —
694	Zr	Cl	2-(2-Fu)	4-Tol	2	2-(2-Fu)	4-Tol	2	—Ge(Me) 2 —
695	Zr	Cl	2-(2-Fu)	4-OBzl	2	2-(2-Fu)	4-OBzl	2	—Ge(Me) 2 —
696	Zr	Cl	2-(2-Fu)	4-TMS	2	2-(2-Fu)	4-TMS	2	—Ge(Me) 2 —
697	Zr	Cl	2-(2-Fu)	4-(1-Pyr)	2	2-(2-Fu)	4-(1-Pyr)	2	—Ge(Me) 2 —
698	Zr	Cl	2-(2-Fu)	4-(1-Indo)	2	2-(2-Fu)	4-(1-Indo)	2	—Ge(Me) 2 —
699	Zr	Cl	2-(2-Fu), 4-(2-Fu)	—	2	2-(2-Fu), 4-(2-Fu)	—	2	—Ge(Me) 2 —
700	Zr	Cl	2-(2-Fu), 4-(2-Thie)	—	2	2-(2-Fu), 4-(2-Thie)	—	2	—Ge(Me) 2 —
701	Zr	Cl	2-(2-Fu), 4-(2-BzFu)	—	2	2-(2-Fu), 4-(2-BzFu)	—	2	—Ge(Me) 2 —
702	Zr	Cl	2-(2-Fu), 4-(2-Py)	—	2	2-(2-Fu), 4-(2-Py)	—	2	—Ge(Me) 2 —
703	Zr	Cl	2-(2-Fu), 4-(1-MePyr)	—	2	2-(2-Fu), 4-(1-MePyr)	—	2	—Ge(Me) 2 —
704	Zr	Cl	2-(2-Fu)	4-Et, 7-Et	3	2-(2-Fu)	4-Et, 7-Et	3	—Ge(Me) 2 —
705	Zr	Cl	2-(2-Fu)	4-I—Pr, 7-I—Pr	3	2-(2-Fu)	4-I—Pr, 7-I—Pr	3	—Ge(Me) 2 —
706	Zr	Cl	2-(2-Fu)	4-t-Bu, 7-t-Bu	3	2-(2-Fu)	4-t-Bu, 7-t-Bu	3	—Ge(Me) 2 —
707	Zr	Cl	2-(2-Fu)	4-Ph, 7-Ph	3	2-(2-Fu)	4-Ph, 7-Ph	3	—Ge(Me) 2 —
708	Zr	Cl	2-(2-Fu)	3-Ph, 7-Me	3	2-(2-Fu)	3-Ph, 7-Me	3	—Ge(Me) 2 —
709	Zr	Cl	2-(2-Fu)	4-Me, 7-Me	3	2-(2-Fu)	4-Me, 7-Me	3	—Ge(Et) 2 —
710	Zr	Cl	2-(2-Fu)	4-Me, 7-Me	3	2-(2-Fu)	4-Me, 7-Me	3	—Ge(Ph) 2 —
711	Zr	Me	2-(2-Fu)	4-Ph	2	2-(2-Fu)	4-Ph	2	—Ge(Me) 2 —
712	Zr	Bzl	2-(2-Fu)	4-Ph	2	2-(2-Fu)	4-Ph	2	—Ge(Me) 2 —
713	Hf	Cl	2-(2-Fu)	4-Ph	2	2-(2-Fu)	4-Ph	2	—Ge(Me) 2 —
714	Ti	Cl	2-(2-Fu)	4-Ph	2	2-(2-Fu)	4-Ph	2	—Ge(Me) 2 —
715	Hf	Cl	2-(2-Fu)	3-Me, 7-Me	3	2-(2-Fu)	3-Me, 7-Me	3	—Ge(Me) 2 —
716	Ti	Cl	2-(2-Fu)	3-Me, 7-Me	3	2-(2-Fu)	3-Me, 7-Me	3	—Ge(Me) 2 —
717	Zr	Cl	2-(3-Fu)	4-Ph	2	2-(3-Fu)	4-Ph	2	—Ge(Me) 2 —
718	Zr	Cl	2-(3-Fu)	4-Ph	2	2-(3-Fu)	4-Ph	2	—Ge(Me) 2 —
719	Zr	Cl	2-[2-(3-Me—Fu)]	4-Ph	2	2-[2-(3-Me—Fu)]	4-Ph	2	—Ge(Me) 2 —
720	Zr	Cl	2-[2-(3-Me—Fu)]	—	1	2-[2-(3-Me—Fu)]	—	1	—Ge(Me) 2 —
721	Zr	Cl	2-(2-Thie)	4-Ph	2	2-(2-Thie)	4-Ph	2	—Ge(Me) 2 —
722	Zr	Cl	2-(2-Thie)	—	1	2-(2-Thie)	—	1	—Ge(Me) 2 —
723	Zr	Cl	2-(2-Py)	4-Ph	2	2-(2-Py)	4-Ph	2	—Ge(Me) 2 —
724	Zr	Cl	2-(2-Py)	—	1	2-(2-Py)	—	1	—Ge(Me) 2 —
725	Zr	Cl	2-(2-BzFu)	4-Ph	2	2-(2-BzFu)	4-Ph	2	—Ge(Me) 2 —
726	Zr	Cl	2-(2-BzFu)	—	1	2-(2-BzFu)	—	1	—Ge(Me) 2 —
727	Zr	Cl	2-[2-(N—Me—Pyr)]	4-Ph	2	2-[2-(N—Me—Pyr)]	4-Ph	2	—Ge(Me) 2 —
728	Zr	Cl	2-[2-(N—Me—Pyr)]	—	1	2-[2-(N—Me—Pyr)]	—	1	—Ge(Me) 2 —

	TABLE 18
	CA 1 : Benzoindenyl	CA 2 : Benzoindenyl
No.	M	X	Ra	R 1	p + m	Ra	R 1	q + n	Y
729	Zr	Cl	2-(2-Fu)	—	1	2-(2-Fu)	—	1	—SiH 2 —
730	Zr	Cl	2-(2-Fu)	—	1	2-(2-Fu)	—	1	—Si(Me) 2 —
731	Zr	Cl	2-(2-Fu)	9-Me	2	2-(2-Fu)	9-Me	2	—Si(Me) 2 —
732	Zr	Cl	2-(2-Fu)	5-Me	2	2-(2-Fu)	5-Me	2	—Si(Me) 2 —
733	Zr	Cl	2-(2-Fu)	3-Me	2	2-(2-Fu)	3-Me	2	—Si(Me) 2 —
734	Zr	Cl	2-(2-Fu)	3-Me, 9-Me	3	2-(2-Fu)	3-Me, 9-Me	3	—Si(Me) 2 —
735	Zr	Cl	2-(2-Fu)	5-Me, 9-Me	3	2-(2-Fu)	5-Me, 9-Me	3	—Si(Me) 2 —
736	Zr	Cl	2-(2-Fu)	5-Cl	2	2-(2-Fu)	5-Cl	2	—Si(Me) 2 —
737	Zr	Cl	2-(2-Fu)	5-Et	2	2-(2-Fu)	5-Et	2	—Si(Me) 2 —
738	Zr	Cl	2-(2-Fu)	5-i-Pr	2	2-(2-Fu)	5-i-Pr	2	—Si(Me) 2 —
739	Zr	Cl	2-(2-Fu)	5-t-Bu	2	2-(2-Fu)	5-t-Bu	2	—Si(Me) 2 —
740	Zr	Cl	2-(2-Fu)	5-Ph	2	2-(2-Fu)	5-Ph	2	—Si(Me) 2 —
741	Zr	Cl	2-(2-Fu)	5-Np	2	2-(2-Fu)	5-Np	2	—Si(Me) 2 —
742	Zr	Cl	2-(2-Fu)	5-OMe	2	2-(2-Fu)	5-OMe	2	—Si(Me) 2 —
743	Zr	Cl	2-(2-Fu)	5-OPh	2	2-(2-Fu)	5-OPh	2	—Si(Me) 2 —
744	Zr	Cl	2-(2-Fu)	5-Bzl	2	2-(2-Fu)	5-Bzl	2	—Si(Me) 2 —
745	Zr	Cl	2-(2-Fu)	5-Tol	2	2-(2-Fu)	5-Tol	2	—Si(Me) 2 —
746	Zr	Cl	2-(2-Fu)	5-OBzl	2	2-(2-Fu)	5-OBzl	2	—Si(Me) 2 —
747	Zr	Cl	2-(2-Fu)	5-TMS	2	2-(2-Fu)	5-TMS	2	—Si(Me) 2 —
748	Zr	Cl	2-(2-Fu)	5-(1-Pyr)	2	2-(2-Fu)	5-(1-Pyr)	2	—Si(Me) 2 —
749	Zr	Cl	2-(2-Fu)	5-(1-Indo)	2	2-(2-Fu)	5-(1-Indo)	2	—Si(Me) 2 —
750	Zr	Cl	2-(2-Fu), 5-(2-Fu)	—	2	2-(2-Fu), 5-(2-Fu)	—	2	—Si(Me) 2 —
751	Zr	Cl	2-(2-Fu), 5-(2-Thie)	—	2	2-(2-Fu), 5-(2-Thie)	—	2	—Si(Me) 2 —
752	Zr	Cl	2-(2-Fu), 5-(2-BzFu)	—	2	2-(2-Fu), 5-(2-BzFu)	—	2	—Si(Me) 2 —
753	Zr	Cl	2-(2-Fu), 5-(2-Py)	—	2	2-(2-Fu), 5-(2-Py)	—	2	—Si(Me) 2 —
754	Zr	Cl	2-(2-Fu), 5-[2-(1-MePyr)]	—	2	2-(2-Fu), 5-[2-(1-MePyr)]	—	2	—Si(Me) 2 —
755	Zr	Cl	2-(2-Fu)	5-Et, 9-Et	3	2-(2-Fu)	5-Et, 9-Et	3	—Si(Me) 2 —
756	Zr	Cl	2-(2-Fu)	5-i-Pr, 9-i-Pr	3	2-(2-Fu)	5-i-Pr, 9-i-Pr	3	—Si(Me) 2 —
757	Zr	Cl	2-(2-Fu)	5-t-Bu, 9-t-Bu	3	2-(2-Fu)	5-t-Bu, 9-t-Bu	3	—Si(Me) 2 —
758	Zr	Cl	2-(2-Fu)	5-Ph, 9-Ph	3	2-(2-Fu)	5-Ph, 9-Ph	3	—Si(Me) 2 —
759	Zr	Cl	2-(2-Fu)	3-Ph, 9-Me	3	2-(2-Fu)	3-Ph, 9-Me	3	—Si(Me) 2 —
760	Zr	Cl	2-(2-Fu)	5-Me, 9-Me	3	2-(2-Fu)	5-Me, 9-Me	3	—Si(Et) 2 —
761	Zr	Cl	2-(2-Fu)	5-Me, 9-Me	3	2-(2-Fu)	5-Me, 9-Me	3	—Si(Ph) 2 —
762	Zr	Me	2-(2-Fu)	5-Ph	2	2-(2-Fu)	5-Ph	2	—Si(Me) 2 —
763	Zr	Bzl	2-(2-Fu)	5-Ph	2	2-(2-Fu)	5-Ph	2	—Si(Me) 2 —
764	Hf	Cl	2-(2-Fu)	5-Ph	2	2-(2-Fu)	5-Ph	2	—Si(Me) 2 —
765	Ti	Cl	2-(2-Fu)	5-Ph	2	2-(2-Fu)	5-Ph	2	—Si(Me) 2 —
766	Hf	Cl	2-(2-Fu)	3-Me, 9-Me	3	2-(2-Fu)	3-Me, 9-Me	3	—Si(Me) 2 —
767	Ti	Cl	2-(2-Fu)	3-Me, 9-Me	3	2-(2-Fu)	3-Me, 9-Me	3	—Si(Me) 2 —
768	Zr	Cl	2-(3-Fu)	5-Ph	2	2-(3-Fu)	5-Ph	2	—Si(Me) 2 —
769	Zr	Cl	2-(3-Fu)	5-Ph	2	2-(3-Fu)	5-Ph	2	—Si(Me) 2 —
770	Zr	Cl	2-[2-(3-Me—Fu)]	5-Ph	2	2-[2-(3-Me—Fu)]	5-Ph	2	—Si(Me) 2 —
771	Zr	Cl	2-[2-(3-Me—Fu)]	—	1	2-[2-(3-Me—Fu)]	—	1	—Si(Me) 2 —
772	Zr	Cl	2-(2-Thie)	5-Ph	2	2-(2-Thie)	5-Ph	2	—Si(Me) 2 —
773	Zr	Cl	2-(2-Thie)	—	1	2-(2-Thie)	—	1	—Si(Me) 2 —
774	Zr	Cl	2-(2-Py)	5-Ph	2	2-(2-Py)	5-Ph	2	—Si(Me) 2 —
775	Zr	Cl	2-(2-Py)	—	1	2-(2-Py)	—	1	—Si(Me) 2 —
776	Zr	Cl	2-(2-BzFu)	5-Ph	2	2-(2-BzFu)	5-Ph	2	—Si(Me) 2 —
777	Zr	Cl	2-(2-BzFu)	—	1	2-(2-BzFu)	—	1	—Si(Me) 2 —
778	Zr	Cl	2-[2-(N—Me—Pyr)]	5-Ph	2	2-[2-(N—Me—Pyr)]	5-Ph	2	—Si(Me) 2 —
779	Zr	Cl	2-[2-(N—Me—Pyr)]	—	1	2-[2-(N—Me—Pyr)]	—	1	—Si(Me) 2 —

	TABLE 19
	CA 1 : Benzoindenyl	CA 2 : Benzoindenyl
No.	M	X	Ra	R 1	p + m	Ra	R 1	q + n	Y
780	Zr	Cl	2-(2-Fu)	—	1	2-(2-Fu)	—	1	—GeH 2 —
781	Zr	Cl	2-(2-Fu)	—	1	2-(2-Fu)	—	1	—Ge(Me) 2 —
782	Zr	Cl	2-(2-Fu)	9-Me	2	2-(2-Fu)	9-Me	2	—Ge(Me) 2 —
783	Zr	Cl	2-(2-Fu)	5-Me	2	2-(2-Fu)	5-Me	2	—Ge(Me) 2 —
784	Zr	Cl	2-(2-Fu)	3-Me	2	2-(2-Fu)	3-Me	2	—Ge(Me) 2 —
785	Zr	Cl	2-(2-Fu)	3-Me, 9-Me	3	2-(2-Fu)	3-Me, 9-Me	3	—Ge(Me) 2 —
786	Zr	Cl	2-(2-Fu)	5-Me, 9-Me	3	2-(2-Fu)	5-Me, 9-Me	3	—Ge(Me) 2 —
787	Zr	Cl	2-(2-Fu)	5-Cl	2	2-(2-Fu)	5-Cl	2	—Ge(Me) 2 —
788	Zr	Cl	2-(2-Fu)	5-Et	2	2-(2-Fu)	5-Et	2	—Ge(Me) 2 —
789	Zr	Cl	2-(2-Fu)	5-i-Pr	2	2-(2-Fu)	5-i-Pr	2	—Ge(Me) 2 —
790	Zr	Cl	2-(2-Fu)	5-t-Bu	2	2-(2-Fu)	5-t-Bu	2	—Ge(Me) 2 —
791	Zr	Cl	2-(2-Fu)	5-Ph	2	2-(2-Fu)	5-Ph	2	—Ge(Me) 2 —
792	Zr	Cl	2-(2-Fu)	5-Np	2	2-(2-Fu)	5-Np	2	—Ge(Me) 2 —
793	Zr	Cl	2-(2-Fu)	5-OMe	2	2-(2-Fu)	5-OMe	2	—Ge(Me) 2 —
794	Zr	Cl	2-(2-Fu)	5-OPh	2	2-(2-Fu)	5-OPh	2	—Ge(Me) 2 —
795	Zr	Cl	2-(2-Fu)	5-Bzl	2	2-(2-Fu)	5-Bzl	2	—Ge(Me) 2 —
796	Zr	Cl	2-(2-Fu)	5-Tol	2	2-(2-Fu)	5-Tol	2	—Ge(Me) 2 —
797	Zr	Cl	2-(2-Fu)	5-OBzl	2	2-(2-Fu)	5-OBzl	2	—Ge(Me) 2 —
798	Zr	Cl	2-(2-Fu)	5-TMS	2	2-(2-Fu)	5-TMS	2	—Ge(Me) 2 —
799	Zr	Cl	2-(2-Fu)	5-(1-Pyr)	2	2-(2-Fu)	5-(1-Pyr)	2	—Ge(Me) 2 —
800	Zr	Cl	2-(2-Fu)	5-(1-Indo)	2	2-(2-Fu)	5-(1-Indo)	2	—Ge(Me) 2 —
801	Zr	Cl	2-(2-Fu), 5-(2-Fu)	—	2	2-(2-Fu), 5-(2-Fu)	—	2	—Ge(Me) 2 —
802	Zr	Cl	2-(2-Fu), 5-(2-Thie)	—	2	2-(2-Fu), 5-(2-Thie)	—	2	—Ge(Me) 2 —
803	Zr	Cl	2-(2-Fu), 5-(2-BzFu)	—	2	2-(2-Fu), 5-(2-BzFu)	—	2	—Ge(Me) 2 —
804	Zr	Cl	2-(2-Fu), 5-(2-Py)	—	2	2-(2-Fu), 5-(2-Py)	—	2	—Ge(Me) 2 —
805	Zr	Cl	2-(2-Fu), 5-[2-(1-MePyr)]	—	2	2-(2-Fu), 5-[2-(1-MePyr)]	—	2	—Ge(Me) 2 —
806	Zr	Cl	2-(2-Fu)	5-Et, 9-Et	3	2-(2-Fu)	5-Et, 9-Et	3	—Ge(Me) 2 —
807	Zr	Cl	2-(2-Fu)	5-i-Pr, 9-i-Pr	3	2-(2-Fu)	5-i-Pr, 9-i-Pr	3	—Ge(Me) 2 —
808	Zr	Cl	2-(2-Fu)	5-t-Bu, 9-t-Bu	3	2-(2-Fu)	5-t-Bu, 9-t-Bu	3	—Ge(Me) 2 —
809	Zr	Cl	2-(2-Fu)	5-Ph, 9-Ph	3	2-(2-Fu)	5-Ph, 9-Ph	3	—Ge(Me) 2 —
810	Zr	Cl	2-(2-Fu)	3-Ph, 9-Me	3	2-(2-Fu)	3-Ph, 9-Me	3	—Ge(Me) 2 —
811	Zr	Cl	2-(2-Fu)	5-Me, 9-Me	3	2-(2-Fu)	5-Me, 9-Me	3	—Ge(Et) 2 —
812	Zr	Cl	2-(2-Fu)	5-Me, 9-Me	3	2-(2-Fu)	5-Me, 9-Me	3	—Ge(Ph) 2 —
813	Zr	Me	2-(2-Fu)	5-Ph	2	2-(2-Fu)	5-Ph	2	—Ge(Me) 2 —
814	Zr	Bzl	2-(2-Fu)	5-Ph	2	2-(2-Fu)	5-Ph	2	—Ge(Me) 2 —
815	Hf	Cl	2-(2-Fu)	5-Ph	2	2-(2-Fu)	5-Ph	2	—Ge(Me) 2 —
816	Ti	Cl	2-(2-Fu)	5-Ph	2	2-(2-Fu)	5-Ph	2	—Ge(Me) 2 —
817	Hf	Cl	2-(2-Fu)	3-Me, 9-Me	3	2-(2-Fu)	3-Me, 9-Me	3	—Ge(Me) 2 —
818	Ti	Cl	2-(2-Fu)	3-Me, 9-Me	3	2-(2-Fu)	3-Me, 9-Me	3	—Ge(Me) 2 —
819	Zr	Cl	2-(3-Fu)	5-Ph	2	2-(3-Fu)	5-Ph	2	—Ge(Me) 2 —
820	Zr	Cl	2-(3-Fu)	5-Ph	2	2-(3-Fu)	5-Ph	2	—Ge(Me) 2 —
821	Zr	Cl	2-[2-(3-Me—Fu)]	5-Ph	2	2-[2-(3-Me—Fu)]	5-Ph	2	—Ge(Me) 2 —
822	Zr	Cl	2-[2-(3-Me—Fu)]	—	1	2-[2-(3-Me—Fu)]	—	1	—Ge(Me) 2 —
823	Zr	Cl	2-(2-Thie)	5-Ph	2	2-(2-Thie)	5-Ph	2	—Ge(Me) 2 —
824	Zr	Cl	2-(2-Thie)	—	1	2-(2-Thie)	—	1	—Ge(Me) 2 —
825	Zr	Cl	2-(2-Py)	5-Ph	2	2-(2-Py)	5-Ph	2	—Ge(Me) 2 —
826	Zr	Cl	2-(2-Py)	—	1	2-(2-Py)	—	1	—Ge(Me) 2 —
827	Zr	Cl	2-(2-BzFu)	5-Ph	2	2-(2-BzFu)	5-Ph	2	—Ge(Me) 2 —
828	Zr	Cl	2-(2-BzFu)	—	1	2-(2-BzFu)	—	1	—Ge(Me) 2 —
829	Zr	Cl	2-[2-(N—Me—Pyr)]	5-Ph	2	2-[2-(N—Me—Pyr)]	5-Ph	2	—Ge(Me) 2 —
830	Zr	Cl	2-[2-(N—Me—Pyr)]	—	1	2-[2-(N—Me—Pyr)]	—	1	—Ge(Me) 2 —

	TABLE 20
	CA 1 : Cyclopentadienyl	Z: —(R 1 )N—
No.	M	X	Ra	R 1	p + m	R 1	Y
831	Ti	Cl	2-(2-Fu)	—	1	t-Bu	—SiH 2 —
832	Ti	Cl	2-(2-Fu)	—	1	t-Bu	—Si(Me) 2 —
833	Ti	Cl	2-(2-Fu)	5-Me	2	t-Bu	—Si(Me) 2 —
834	Ti	Cl	2-(2-Fu)	4-Me	2	t-Bu	—Si(Me) 2 —
835	Ti	Cl	2-(2-Fu)	4-OMe	2	t-Bu	—Si(Me) 2 —
836	Ti	Cl	2-(2-Fu)	4-OPh	2	t-Bu	—Si(Me) 2 —
837	Ti	Cl	2-(2-Fu)	4-Bzl	2	t-Bu	—Si(Me) 2 —
838	Ti	Cl	2-(2-Fu)	4-Tol	2	t-Bu	—Si(Me) 2 —
839	Ti	Cl	2-(2-Fu)	4-OBzl	2	t-Bu	—Si(Me) 2 —
840	Ti	Cl	2-(2-Fu)	4-TMS	2	t-Bu	—Si(Me) 2 —
841	Ti	Cl	2-(2-Fu)	4-(1-Pyr)	2	t-Bu	—Si(Me) 2 —
842	Ti	Cl	2-(2-Fu)	4-(1-Indo)	2	t-Bu	—Si(Me) 2 —
843	Ti	Cl	2-(2-Fu)	3-Me	2	t-Bu	—Si(Me) 2 —
844	Ti	Cl	2-(2-Fu)	3-Me, 5-Me	3	t-Bu	—Si(Me) 2 —
845	Ti	Cl	2-(2-Fu)	4-Me, 5-Me	3	t-Bu	—Si(Me) 2 —
846	Ti	Cl	2-(2-Fu)	4-Et, 5-Me	3	t-Bu	—Si(Me) 2 —
847	Ti	Cl	2-(2-Fu)	4-(i-Pr), 5-Me	3	t-Bu	—Si(Me) 2 —
848	Ti	Cl	2-(2-Fu)	4-(t-Bu), 5-Me	3	t-Bu	—Si(Me) 2 —
849	Ti	Cl	2-(2-Fu)	4-Ph, 5-Me	3	t-Bu	—Si(Me) 2 —
850	Ti	Cl	2-(2-Fu)	3-Ph, 5-Me	3	t-Bu	—Si(Me) 2 —
851	Ti	Cl	2-(2-Fu)	4-Me, 5-Me	3	Ph	—Si(Me) 2 —
852	Ti	Cl	2-(2-Fu)	4-Me, 5-Me	3	Me	—Si(Et) 2 —
853	Ti	Cl	2-(2-Fu)	4-Me, 5-Me	3	Me	—Si(Ph) 2 —
854	Ti	Me	2-(2-Fu)	4-Me, 5-Me	3	Me	—Si(Me) 2 —
855	Ti	Bzl	2-(2-Fu)	4-Me, 5-Me	3	Me	—Si(Me) 2 —
856	Hf	Cl	2-(2-Fu)	4-Me, 5-Me	3	Me	—Si(Me) 2 —
857	Zr	Cl	2-(2-Fu)	4-Me, 5-Me	3	Me	—Si(Me) 2 —
858	Hf	Cl	2-(2-Fu)	3-Me, 5-Me	3	Me	—Si(Me) 2 —
859	Zr	Cl	2-(2-Fu)	3-Me, 5-Me	3	Me	—Si(Me) 2 —
860	Hf	Cl	2-(2-Fu)	4-Me, 5-Me	3	t-Bu	—Si(Me) 2 —
861	Zr	Cl	2-(2-Fu)	4-Me, 5-Me	3	t-Bu	—Si(Me) 2 —
862	Hf	Cl	2-(2-Fu)	3-Me, 5-Me	3	t-Bu	—Si(Me) 2 —
863	Zr	Cl	2-(2-Fu)	3-Me, 5-Me	3	t-Bu	—Si(Me) 2 —
864	Ti	Cl	2-(3-Fu)	4-Me, 5-Me	3	t-Bu	—Si(Me) 2 —
865	Ti	Cl	2-(3-Fu)	3-Me, 5-Me	3	Me	—Si(Me) 2 —
866	Ti	Cl	2-[2-(3-Me—Fu)]	4-Me, 5-Me	3	t-Bu	—Si(Me) 2 —
867	Ti	Cl	2-[2-(3-Me—Fu)]	3-Me, 5-Me	3	Me	—Si(Me) 2 —
868	Ti	Cl	2-(2-Thie)	4-Me, 5-Me	3	t-Bu	—Si(Me) 2 —
869	Ti	Cl	2-(2-Thie)	3-Me, 5-Me	3	Me	—Si(Me) 2 —
870	Ti	Cl	2-(2-Py)	4-Me, 5-Me	3	t-Bu	—Si(Me) 2 —
871	Ti	Cl	2-(2-Py)	3-Me, 5-Me	3	Me	—Si(Me) 2 —
872	Ti	Cl	2-(2-BzFu)	4-Me, 5-Me	3	t-Bu	—Si(Me) 2 —
873	Ti	Cl	2-(2-BzFu)	3-Me, 5-Me	3	Me	—Si(Me) 2 —
874	Ti	Cl	2-[2-(1-Me—Pyr)]	4-Me, 5-Me	3	t-Bu	—Si(Me) 2 —
875	Ti	Cl	2-[2-(1-Me—Pyr)]	3-Me, 5-Me	3	Me	—Si(Me) 2 —

	TABLE 21
	CA 1 : Cyclopentadienyl	Z: —(R 1 )N—
No.	M	X	Ra	R 1	p + m	R 1	Y
876	Ti	Cl	2-(2-Fu)	—	1	t-Bu	—GeH 2 —
877	Ti	Cl	2-(2-Fu)	—	1	t-Bu	—Ge(Me) 2 —
878	Ti	Cl	2-(2-Fu)	5-Me	2	t-Bu	—Ge(Me) 2 —
879	Ti	Cl	2-(2-Fu)	4-Me	2	t-Bu	—Ge(Me) 2 —
880	Ti	Cl	2-(2-Fu)	4-Ome	2	t-Bu	—Ge(Me) 2 —
881	Ti	Cl	2-(2-Fu)	4-Oph	2	t-Bu	—Ge(Me) 2 —
882	Ti	Cl	2-(2-Fu)	4-Bzl	2	t-Bu	—Ge(Me) 2 —
883	Ti	Cl	2-(2-Fu)	4-Tol	2	t-Bu	—Ge(Me) 2 —
884	Ti	Cl	2-(2-Fu)	4-OBzl	2	t-Bu	—Ge(Me) 2 —
885	Ti	Cl	2-(2-Fu)	4-TMS	2	t-Bu	—Ge(Me) 2 —
886	Ti	Cl	2-(2-Fu)	4-(1-Pyr)	2	t-Bu	—Ge(Me) 2 —
887	Ti	Cl	2-(2-Fu)	4-(1-Indo)	2	t-Bu	—Ge(Me) 2 —
888	Ti	Cl	2-(2-Fu)	3-Me	2	t-Bu	—Ge(Me) 2 —
889	Ti	Cl	2-(2-Fu)	3-Me, 5-Me	3	t-Bu	—Ge(Me) 2 —
890	Ti	Cl	2-(2-Fu)	4-Me, 5-Me	3	t-Bu	—Ge(Me) 2 —
891	Ti	Cl	2-(2-Fu)	4-Et, 5-Me	3	t-Bu	—Ge(Me) 2 —
892	Ti	Cl	2-(2-Fu)	4-(i-Pr), 5-Me	3	t-Bu	—Ge(Me) 2 —
893	Ti	Cl	2-(2-Fu)	4-(t-Bu), 5-Me	3	t-Bu	—Ge(Me) 2 —
894	Ti	Cl	2-(2-Fu)	4-Ph, 5-Me	3	t-Bu	—Ge(Me) 2 —
895	Ti	Cl	2-(2-Fu)	3-Ph, 5-Me	3	t-Bu	—Ge(Me) 2 —
896	Ti	Cl	2-(2-Fu)	4-Me, 5-Me	3	Ph	—Ge(Me) 2 —
897	Ti	Cl	2-(2-Fu)	4-Me, 5-Me	3	Me	—Ge(Et) 2 —
898	Ti	Cl	2-(2-Fu)	4-Me, 5-Me	3	Me	—Ge(Ph) 2 —
899	Ti	Me	2-(2-Fu)	4-Me, 5-Me	3	Me	—Ge(Me) 2 —
900	Ti	Bzl	2-(2-Fu)	4-Me, 5-Me	3	Me	—Ge(Me) 2 —
901	Hf	Cl	2-(2-Fu)	4-Me, 5-Me	3	Me	—Ge(Me) 2 —
902	Zr	Cl	2-(2-Fu)	4-Me, 5-Me	3	Me	—Ge(Me) 2 —
903	Hf	Cl	2-(2-Fu)	3-Me, 5-Me	3	Me	—Ge(Me) 2 —
904	Zr	Cl	2-(2-Fu)	3-Me, 5-Me	3	Me	—Ge(Me) 2 —
905	Hf	Cl	2-(2-Fu)	4-Me, 5-Me	3	t-Bu	—Ge(Me) 2 —
906	Zr	Cl	2-(2-Fu)	4-Me, 5-Me	3	t-Bu	—Ge(Me) 2 —
907	Hf	Cl	2-(2-Fu)	3-Me, 5-Me	3	t-Bu	—Ge(Me) 2 —
908	Zr	Cl	2-(2-Fu)	3-Me, 5-Me	3	t-Bu	—Ge(Me) 2 —
909	Ti	Cl	2-(3-Fu)	4-Me, 5-Me	3	t-Bu	—Ge(Me) 2 —
910	Ti	Cl	2-(3-Fu)	3-Me, 5-Me	3	Me	—Ge(Me) 2 —
911	Ti	Cl	2-[2-(3-Me—Fu)]	4-Me, 5-Me	3	t-Bu	—Ge(Me) 2 —
912	Ti	Cl	2-[2-(3-Me—Fu)]	3-Me, 5-Me	3	Me	—Ge(Me) 2 —
913	Ti	Cl	2-(2-Thie)	4-Me, 5-Me	3	t-Bu	—Ge(Me) 2 —
914	Ti	Cl	2-(2-Thie)	3-Me, 5-Me	3	Me	—Ge(Me) 2 —
915	Ti	Cl	2-(2-Py)	4-Me, 5-Me	3	t-Bu	—Ge(Me) 2 —
916	Ti	Cl	2-(2-Py)	3-Me, 5-Me	3	Me	—Ge(Me) 2 —
917	Ti	Cl	2-(2-BzFu)	4-Me, 5-Me	3	t-Bu	—Ge(Me) 2 —
918	Ti	Cl	2-(2-BzFu)	3-Me, 5-Me	3	Me	—Ge(Me) 2 —
919	Ti	Cl	2-[2-(1-Me—Pyr)]	4-Me, 5-Me	3	t-Bu	—Ge(Me) 2 —
920	Ti	Cl	2-[2-(1-Me—Pyr)]	3-Me, 5-Me	3	Me	—Ge(Me) 2 —

	TABLE 22
	CA 1 : Indenyl	CA 2 : Indenyl
No.	M	X	Ra	R 1	p + m	Ra	R 1	q + n	Y
921	Zr	Cl	2-[2-(5-Me—Fu)]	—	1	2-[2-(5-Me—Fu)]	—	1	—Si(Me) 2 —
922	Zr	Cl	2-[2-(4,5-Me 2 —Fu)]	—	1	2-[2-(4,5-Me 2 —Fu)]	—	1	—Si(Me) 2 —
923	Zr	Cl	2-[2-(5-t-Bu—Fu)]	—	1	2-[2-(5-t-Bu—Fu)]	—	1	—Si(Me) 2 —
924	Zr	Cl	2-[2-(5-TMS—Fu)]	—	1	2-[2-(5-TMS—Fu)]	—	1	—Si(Me) 2 —
925	Zr	Cl	2-[2-(5-ViMe 2 Si—Fu)]	—	1	2-[2-(5-ViMe 2 Si—Fu)]	—	1	—Si(Me) 2 —
926	Zr	Cl	2-[2-(5-Me—Fu)]	4-Ph	2	2-[2-(5-Me—Fu)]	4-Ph	2	—Si(Me) 2 —
927	Zr	Cl	2-[2-(4,5-Me 2 —Fu)]	4-Ph	2	2-[2-(4,5-Me 2 —Fu)]	4-Ph	2	—Si(Me) 2 —
928	Zr	Cl	2-[2-(5-t-Bu—Fu)]	4-Ph	2	2-[2-(5-t-Bu—Fu)]	4-Ph	2	—Si(Me) 2 —
929	Zr	Cl	2-[2-(5-TMS—Fu)]	4-Ph	2	2-[2-(5-TMS—Fu)]	4-Ph	2	—Si(Me) 2 —
930	Zr	Cl	2-[2-(5-ViMe 2 Si—Fu)]	4-Ph	2	2-[2-(5-ViMe 2 Si—Fu)]	4-Ph	2	—Si(Me) 2 —
931	Zr	Cl	2-[2-(5-Me—Fu)]	4-Np	2	2-[2-(5-Me—Fu)]	4-Np	2	—Si(Me) 2 —
932	Zr	Cl	2-[2-(4,5-Me 2 —Fu)]	4-Np	2	2-[2-(4,5-Me 2 —Fu)]	4-Np	2	—Si(Me) 2 —
933	Zr	Cl	2-[2-(5-t-Bu—Fu)]	4-Np	2	2-[2-(5-t-Bu—Fu)]	4-Np	2	—Si(Me) 2 —
934	Zr	Cl	2-[2-(5-TMS—Fu)]	4-Np	2	2-[2-(5-TMS—Fu)]	4-Np	2	—Si(Me) 2 —
935	Zr	Cl	2-[2-(5-ViMe 2 Si—Fu)]	4-Np	2	2-[2-(5-ViMe 2 Si—Fu)]	4-Np	2	—Si(Me) 2 —

	TABLE 22
	CA 1 : Indenyl	CA 2 : Indenyl
No.	M	X	Ra	R 1	p + m	Ra	R 1	q + n	Y
921	Zr	Cl	2-[2-(5-Me—Fu)]	—	1	2-[2-(5-Me—Fu)]	—	1	—Si(Me) 2 —
922	Zr	Cl	2-[2-(4,5-Me 2 —Fu)]	—	1	2-[2-(4,5-Me 2 —Fu)]	—	1	—Si(Me) 2 —
923	Zr	Cl	2-[2-(5-t-Bu—Fu)]	—	1	2-[2-(5-t-Bu—Fu)]	—	1	—Si(Me) 2 —
924	Zr	Cl	2-[2-(5-TMS—Fu)]	—	1	2-[2-(5-TMS—Fu)]	—	1	—Si(Me) 2 —
925	Zr	Cl	2-[2-(5-ViMe 2 Si—Fu)]	—	1	2-[2-(5-ViMe 2 Si—Fu)]	—	1	—Si(Me) 2 —
926	Zr	Cl	2-[2-(5-Me—Fu)]	4-Ph	2	2-[2-(5-Me—Fu)]	4-Ph	2	—Si(Me) 2 —
927	Zr	Cl	2-[2-(4,5-Me 2 —Fu)]	4-Ph	2	2-[2-(4,5-Me 2 —Fu)]	4-Ph	2	—Si(Me) 2 —
928	Zr	Cl	2-[2-(5-t-Bu—Fu)]	4-Ph	2	2-[2-(5-t-Bu—Fu)]	4-Ph	2	—Si(Me) 2 —
929	Zr	Cl	2-[2-(5-TMS—Fu)]	4-Ph	2	2-[2-(5-TMS—Fu)]	4-Ph	2	—Si(Me) 2 —
930	Zr	Cl	2-[2-(5-ViMe 2 Si—Fu)]	4-Ph	2	2-[2-(5-ViMe 2 Si—Fu)]	4-Ph	2	—Si(Me) 2 —
931	Zr	Cl	2-[2-(5-Me—Fu)]	4-Np	2	2-[2-(5-Me—Fu)]	4-Np	2	—Si(Me) 2 —
932	Zr	Cl	2-[2-(4,5-Me 2 —Fu)]	4-Np	2	2-[2-(4,5-Me 2 —Fu)]	4-Np	2	—Si(Me) 2 —
933	Zr	Cl	2-[2-(5-t-Bu—Fu)]	4-Np	2	2-[2-(5-t-Bu—Fu)]	4-Np	2	—Si(Me) 2 —
934	Zr	Cl	2-[2-(5-TMS—Fu)]	4-Np	2	2-[2-(5-TMS—Fu)]	4-Np	2	—Si(Me) 2 —
935	Zr	Cl	2-[2-(5-ViMe 2 Si—Fu)]	4-Np	2	2-[2-(5-ViMe 2 Si—Fu)]	4-Np	2	—Si(Me) 2 —

	TABLE 22
	CA 1 : Indenyl	CA 2 : Indenyl
No.	M	X	Ra	R 1	p + m	Ra	R 1	q + n	Y
921	Zr	Cl	2-[2-(5-Me—Fu)]	—	1	2-[2-(5-Me—Fu)]	—	1	—Si(Me) 2 —
922	Zr	Cl	2-[2-(4,5-Me 2 —Fu)]	—	1	2-[2-(4,5-Me 2 —Fu)]	—	1	—Si(Me) 2 —
923	Zr	Cl	2-[2-(5-t-Bu—Fu)]	—	1	2-[2-(5-t-Bu—Fu)]	—	1	—Si(Me) 2 —
924	Zr	Cl	2-[2-(5-TMS—Fu)]	—	1	2-[2-(5-TMS—Fu)]	—	1	—Si(Me) 2 —
925	Zr	Cl	2-[2-(5-ViMe 2 Si—Fu)]	—	1	2-[2-(5-ViMe 2 Si—Fu)]	—	1	—Si(Me) 2 —
926	Zr	Cl	2-[2-(5-Me—Fu)]	4-Ph	2	2-[2-(5-Me—Fu)]	4-Ph	2	—Si(Me) 2 —
927	Zr	Cl	2-[2-(4,5-Me 2 —Fu)]	4-Ph	2	2-[2-(4,5-Me 2 —Fu)]	4-Ph	2	—Si(Me) 2 —
928	Zr	Cl	2-[2-(5-t-Bu—Fu)]	4-Ph	2	2-[2-(5-t-Bu—Fu)]	4-Ph	2	—Si(Me) 2 —
929	Zr	Cl	2-[2-(5-TMS—Fu)]	4-Ph	2	2-[2-(5-TMS—Fu)]	4-Ph	2	—Si(Me) 2 —
930	Zr	Cl	2-[2-(5-ViMe 2 Si—Fu)]	4-Ph	2	2-[2-(5-ViMe 2 Si—Fu)]	4-Ph	2	—Si(Me) 2 —
931	Zr	Cl	2-[2-(5-Me—Fu)]	4-Np	2	2-[2-(5-Me—Fu)]	4-Np	2	—Si(Me) 2 —
932	Zr	Cl	2-[2-(4,5-Me 2 —Fu)]	4-Np	2	2-[2-(4,5-Me 2 —Fu)]	4-Np	2	—Si(Me) 2 —
933	Zr	Cl	2-[2-(5-t-Bu—Fu)]	4-Np	2	2-[2-(5-t-Bu—Fu)]	4-Np	2	—Si(Me) 2 —
934	Zr	Cl	2-[2-(5-TMS—Fu)]	4-Np	2	2-[2-(5-TMS—Fu)]	4-Np	2	—Si(Me) 2 —
935	Zr	Cl	2-[2-(5-ViMe 2 Si—Fu)]	4-Np	2	2-[2-(5-ViMe 2 Si—Fu)]	4-Np	2	—Si(Me) 2 —

	TABLE 25
	CA 1 : Azulenyl	CA 2 : Azulenyl
No.	M	X	Ra	R 1	p + m	Ra	R 1	q + n	Y
956	Zr	Cl	2-(2-Fu)	—	1	2-(2-Fu)	—	1	—Si(Me) 2 —
957	Zr	Cl	2-(2-Fu)	—	1	2-(2-Fu)	—	1	—Si(Me) 2 —
958	Zr	Cl	2-[2-(5-Me—Fu)]	—	1	2-[2-(5-Me—Fu)]	—	1	—Si(Me) 2 —
959	Zr	Cl	2-[2-(4,5-Me 2 —Fu)]	—	1	2-[2-(4,5-Me 2 —Fu)]	—	1	—Si(Me) 2 —
960	Zr	Cl	2-[2-(5-t-Bu—Fu)]	—	1	2-[2-(5-t-Bu—Fu)]	—	1	—Si(Me) 2 —
961	Zr	Cl	2-[2-(5-TMS—Fu)]	—	1	2-[2-(5-TMS—Fu)]	—	1	—Si(Me) 2 —
962	Zr	Cl	2-[2-(5-ViMe 2 Si—Fu)]	—	1	2-[2-(5-ViMe 2 Si—Fu)]	—	1	—Si(Me) 2 —
963	Zr	Cl	2-(2-Fu)	4-Ph	2	2-(2-Fu)	4-Ph	2	—Si(Me) 2 —
964	Zr	Cl	2-(2-BzFu)	4-Ph	2	2-(2-BzFu)	4-Ph	2	—Si(Me) 2 —
965	Zr	Cl	2-[2-(5-Me—Fu)]	4-Ph	2	2-[2-(5-Me—Fu)]	4-Ph	2	—Si(Me) 2 —
966	Zr	Cl	2-[2-(4,5-Me 2 —Fu)]	4-Ph	2	2-[2-(4,5-Me 2 —Fu)]	4-Ph	2	—Si(Me) 2 —
967	Zr	Cl	2-[2-(5-t-Bu—Fu)]	4-Ph	2	2-[2-(5-t-Bu—Fu)]	4-Ph	2	—Si(Me) 2 —
968	Zr	Cl	2-[2-(5-TMS—Fu)]	4-Ph	2	2-[2-(5-TMS—Fu)]	4-Ph	2	—Si(Me) 2 —
969	Zr	Cl	2-[2-(5-ViMe 2 Si—Fu)]	4-Ph	2	2-[2-(5-ViMe 2 Si—Fu)]	4-Ph	2	—Si(Me) 2 —
970	Zr	Cl	2-(2-Fu)	4-Np	2	2-(2-Fu)	4-Np	2	—Si(Me) 2 —
971	Zr	Cl	2-(2-BzFu)	4-Np	2	2-(2-BzFu)	4-Np	2	—Si(Me) 2 —
972	Zr	Cl	2-[2-(5-Me—Fu)]	4-Np	2	2-[2-(5-Me—Fu)]	4-Np	2	—Si(Me) 2 —
973	Zr	Cl	2-[2-(4,5-Me 2 —Fu)]	4-Np	2	2-[2-(4,5-Me 2 —Fu)]	4-Np	2	—Si(Me) 2 —
974	Zr	Cl	2-[2-(5-t-Bu—Fu)]	4-Np	2	2-[2-(5-t-Bu—Fu)]	4-Np	2	—Si(Me) 2 —
975	Zr	Cl	2-[2-(5-TMS—Fu)]	4-Np	2	2-[2-(5-TMS—Fu)]	4-Np	2	—Si(Me) 2 —
976	Zr	Cl	2-[2-(5-ViMe 2 Si—Fu)]	4-Np	2	2-[2-(5-ViMe 2 Si—Fu)]	4-Np	2	—Si(Me) 2 —
977	Zr	Cl	4-(2-Fu)	—	1	4-(2-Fu)	—	1	—Si(Me) 2 —
978	Zr	Cl	4-(2-BzFu)	—	1	4-(2-BzFu)	—	1	—Si(Me) 2 —
979	Zr	Cl	4-[2-(5-Me—Fu)]	—	1	4-[2-(5-Me—Fu)]	—	1	—Si(Me) 2 —
980	Zr	Cl	4-[2-(4,5-Me 2 —Fu)]	—	1	4-[2-(4,5-Me 2 —Fu)]	—	1	—Si(Me) 2 —
981	Zr	Cl	4-[2-(5-t-Bu—Fu)]	—	1	4-[2-(5-t-Bu—Fu)]	—	1	—Si(Me) 2 —
982	Zr	Cl	4-[2-(5-TMS—Fu)]	—	1	4-[2-(5-TMS—Fu)]	—	1	—Si(Me) 2 —
983	Zr	Cl	4-[2-(5-ViMe 2 Si—Fu)]	—	1	4-[2-(5-ViMe 2 Si—Fu)]	—	1	—Si(Me) 2 —
984	Zr	Cl	4-[2-(5-ViMe 2 Si—Fu)]	—	1	4-[2-(5-ViMe 2 Si—Fu)]	—	1	—Si(Me) 2 —
985	Zr	Cl	4-(2-Fu)	2-Me	2	4-(2-Fu)	2-Me	2	—Si(Me) 2 —
986	Zr	Cl	4-(2-BzFu)	2-Me	2	4-(2-BzFu)	2-Me	2	—Si(Me) 2 —
987	Zr	Cl	4-[2-(5-Me—Fu)]	2-Me	2	4-[2-(5-Me—Fu)]	2-Me	2	—Si(Me) 2 —
988	Zr	Cl	4-[2-(4,5-Me 2 —Fu)]	2-Me	2	4-[2-(4,5-Me 2 —Fu)]	2-Me	2	—Si(Me) 2 —
989	Zr	Cl	4-[2-(5-t-Bu—Fu)]	2-Me	2	4-[2-(5-t-Bu—Fu)]	2-Me	2	—Si(Me) 2 —
990	Zr	Cl	4-[2-(5-TMS—Fu)]	2-Me	2	4-[2-(5-TMS—Fu)]	2-Me	2	—Si(Me) 2 —
991	Zr	Cl	4-[2-(5-ViMe 2 Si—Fu)]	2-Me	2	4-[2-(5-ViMe 2 Si—Fu)]	2-Me	2	—Si(Me) 2 —

Claims

1. A metallocene compound represented by the following formula (1) wherein CA1 represents a cycloalkadienyl group selected from the group consisting of a cyclopentadienyl group, an indenyl group, a tetrahydroindenyl group, a benzoindenyl group, a fluorenyl group and an azulenyl group;each R1 represents independently a halogen atom, a hydrocarbon group of 1-20 carbons, a halogenated hydrocarbon group, a silyl group substituted by said hydrocarbon group or said halogenated hydrocarbon group, an amino group substituted by said hydrocarbon group or a monocyclic or polycyclic amino group; each Ra represents independently a monocyclic or polycyclic heteroaromatic group containing a heteroatom selected from the group consisting of an oxygen atom, a sulfur atom and a nitrogen atom in a 5- or 6-membered ring, the heteroaromatic group being optionally substituted by R1 as defined above, provided that the heteroatom in Ra is not directly attached to the 6-membered ring in the cycloalkadienyl group (CA1, CA2); p is an integer of 1-8; m is 0 or an integer of 1-8; Z represents a linking group selected from the group consisting of (CA1)(R1)m(Ra)p, (CA2)(Ra)q(R1)n, —O—, —S—, —NR1— and —PR1— wherein CA2 represents an unsubstituted or substituted cycloalkadienyl group; CA1, m, p, Ra and R1 have the same meanings as defined above, Ra may be identical with or different from said Ra on CA1 and R1 may be identical with or different from said R1 on CA1; and q and n are each independently 0 or an integer of 1-8; Y represents a divalent linking group selected from the group consisting of —C(R2)2—, —C2(R2)4—, —C6(R2)10—, —C6(R2)4—, —Si(R2)2—, —Ge(R2)2— and —Sn(R2)2— wherein each R2 represents independently a hydrogen atom, a halogen atom, a hydrocarbon group of 1-20 carbons, a halogenated hydrocarbon group or a silyl group substituted by said hydrocarbon group or said halogenated hydrocarbon group; M represents a transition metal atom selected from the group consisting of Ti, Zr and Hf; and each X1 represents independently a halogen atom, a hydrocarbon group of 1-20 carbons, a halogenated hydrocarbon group or a silyl group substituted by said hydrocarbon group or said halogenated hydrocarbon group.

2. The metallocene compound of claim 1 wherein Z represents (CA2)(Ra)q(R1)n, which is represented by the following formula (2) wherein CA1, CA2, Ra, R1, p, q, m, n, Y, M and X1 have each the meanings as defined above.

3. The metallocene compound of claim 1 wherein Z represents (CA1)(R1)m(Ra)p, which is represented by the following formula (2A) wherein CA1, Ra, R1, p, m, Y, M and X1 have each the meanings as defined above.

4. The metallocene compound of claim 1 wherein at least one of Ra is substituted on the 5-membered ring in the cycloalkadienyl group.

5. The metallocene compound of claim 1 wherein at least one of Ra is substituted at the 2- or 3-position of a cyclopentadienyl group, an indenyl group, a tetrahydroindenyl group, a benzoindenyl group or an azulenyl group.

6. The metallocene compound of claim 1 wherein each Ra is independently an unsubstituted heteroaromatic group and is selected from the group consisting of furyl, thienyl, pyridyl, benzofuryl, benzothienyl, quinolyl, pyrrolyl and indolyl.

7. The metallocene compound of claim 1 wherein each Ra is independently a heteroaromatic group substituted by R1 as defined above and is selected from the group consisting of substituted furyl, substituted thienyl, substituted pyridyl, substituted benzofuryl, substituted benzothienyl, substituted quinolyl, substituted pyrrolyl and substituted indolyl.

8. The metallocene compound of claim 1 wherein the hydrocarbon group of 1-20 carbons as defined for R1, R2 and X1 is an alkyl group of 1-20 carbons, an aryl group of 6-20 carbons, an aralkyl group of 7-20 carbons, an alkoxy group of 1-20 carbons, an aryloxy group of 6-20 carbons or an aralkyloxy group of 7-20 carbons.

9. The metallocene compound of claim 1 wherein each of CA1 and CA2 is a cyclopentadienyl group or an indenyl group;Ra is furyl or thienyl present at the 2-position of CA1 and CA2 or furyl or thienyl present at the 3-position of CA1 and CA2; M is Ti, Zr or Hf; X1 is a chlorine atom; and Y is a dimethylsilylene group.

10. The metallocene compound of claim 1 wherein each of CA1 and CA2 is a cyclopentadienyl group;Ra is substituted furyl present at the 2-position of CA1 and CA2; M is Ti, Zr or Hf; X1 is a chlorine atom; and Y is a dimethylsilylene group.

11. The metallocene compound of claim 1 wherein Z is —NR1—, which is represented by the following formula (3a) wherein CA1, Ra, R1, p, m, Y, M and X1 have respectively the meanings as defined above.

12. A process for the preparation of the metallocene compound of claim 1, which comprises:(a) reacting a substituted cycloalkadiene anion represented by the following formula (4Aa) (Ra)p(R1)m(CA1)−—  (4Aa) with a binding agent represented by the following formula (5A) at a molar ratio of 2:1,X2—Y—X2  (5A) wherein Y has the meaning as defined above and X2 represents a hydrogen atom or a halogen atom, said substituted cycloalkadiene anion being prepared by reacting a substituted cycloalkadiene represented by the following formula (4A)(Ra)p(R1)m(CA1)H  (4A) wherein CA1, Ra, R1, p and m have respectively the meanings as defined above, with a metal salt type base to effect an anionization; orreacting a substituted cycloalkadiene anion represented by following formula (4Aa) with any one of the compounds represented by the following formulas (5B) to (5F) at a molar ratio of 1:1, X2—Y—(CA2)(R1)n(Ra)q  (5B) X2—Y—(R1)NH  (5C) X2—Y—OH  (5D) X2—Y—SH  (5E) X2—Y—(R1)PH  (5F) in which Y, CA2, Ra, R1 and X2 have respectively the meanings as defined above, to form a compound represented by the following formula (6)(Ra)p(R1)m(CA1)—Y—Z1  (6) wherein Z1 represents (CA1)(R1)m(Ra)p, (CA2)(R1)n(Ra)q, (R1)NH, —OH, —SH or (R1)PH, and then(b) reacting a dianion represented by the following formula (6A) (Ra)p(R1)m(CA1)−—Y—Z−—  (6A) wherein each symbol has the meaning as defined above, with a transition metal compound represented by the following formula (7)(X1)2—M—(X3)2  (7) wherein M and X1 have the meaning as defined above and X1 represents hydrogen or a halogen atom, said dianion being prepared by reacting the compound represented by said formula (6) with a metal salt type base to anionize each of the cycloalkadienyl ring and Z1.

13. The process of claim 12 wherein the substituted cycloalkadiene anion and the binding agent represented by said formula (5A) are allowed to react at a molar ratio of 2:1 in step (a) to produce the metallocene compound of claim 3.

14. The process of claim 12 wherein the substituted cycloalkadiene anion and the compound represented by said formula (5B) are allowed to react at a molar ratio of 1:1 in step (a) to produce the metallocene compound of claim 2.

15. The process of claim 12 wherein the compound represented by said formula (5B) is prepared by reacting a substituted cycloalkadiene anion represented by the following formula (4Ba)—−(CA2)(R1)n(Ra)q  (4Ba) wherein each symbol has the meaning as defined above with a binding agent represented by said formula (5A) at a molar ratio of 1:1, said cycloalkadiene anion being prepared by reacting a substituted cycloalkadiene represented by the following formula (4B)H(CA2)(R1)n(Ra)q  (4B) wherein each symbol has the meaning as defined above, with a metal salt type base to effect an anionization.

16. The process of claim 12 wherein each of Ra in formulas (4A) and (5B) is independently furyl, thienyl, pyridyl, benzofuryl, benzothienyl, quinolyl, pyrrolyl having a bond at other positions than 1-position, or indolyl.

17. The process of claim 12 wherein the compound represented by formula (5A) is dialkyldichloromethane, tetraalkyl-1,2-dichloroethane, dialkyldichlorosilane, dialkyldichlorogermane or dialkyldichlorotin.

18. The process of claim 12 wherein the transition metal compound represented by formula (7) is titanium tetrachloride, dialkyl titanium dichloride, zirconium tetrachloride, dialkyl zirconium dichloride, hafnium tetrachloride or dialkyl hafnium dichloride.

19. The process of claim 12 wherein the metal salt type base is methyllithium, n-butyllithium, t-butyllithium, lithium hydride, sodium hydride or potassium hydride.

20. A catalyst for olefin polymerization comprising the metallocene compound of claim 1 and an aluminoxane.

21. A catalyst for olefin polymerization comprising the metallocene compound of claim 1, an aluminoxane and a support in the form of finely divided particles.

22. The catalyst of claim 21 wherein a reaction product of the metallocene compound and the aluminoxane is carried on the support.

23. The catalyst of claim 21 wherein the support is finely divided inorganic particles.

24. A process for the production of an olefin polymer which comprises polymerizing an olefin in the presence of the catalyst as defined in claim 20.

25. The process of claim 24 wherein the olefin is propylene or a mixed olefin of propylene and other olefins than propylene.

26. A process for the production of an olefin polymer which comprises polymerizing an olefin in the presence of the catalyst as defined in claim 21 and an organic aluminum compound.

27. The process of claim 26 wherein the olefin is propylene or a mixed olefin of propylene and other olefins than propylene.

28. The process of claim 26 wherein the organic aluminum compound is triethylaluminum or tri-iso-butylaluminum.

29. The metallocene compound of claim 1 wherein at least one of Ra is substituted on the 5-membered ring in the cycloalkadienyl group and Ra is selected from the group consisting of furyl, benzofuryl, thienyl and benzothienyl.

30. The metallocene compound of claim 1 wherein at least one of Ra is substituted on the 5-membered ring in the cycloalkadienyl group, Ra is selected from the group consisting of furyl, benzofuryl, thienyl and benzothienyl and M is Ti, Zr or Hf.