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

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 consisting of complex compounds wherein a cycloalkadienyl ring-containing multidentate compound substituted on the ring by a heteroaromatic group containing an oxygen, a sulfur or a nitrogen atom is coordinated to a Group VIB transition metal atom 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 π-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 substituted cycloalkadienyl group selected from the group consisting of a substituted cyclopentadienyl group, a substituted indenyl group, a substituted tetrahydroindenyl group, a substituted benzoindenyl group and a substituted fluorenyl 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; 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;

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

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, and a process for the preparation thereof.

Further, the invention provides a catalyst for olefin polymerization comprising said metallocene compound and an aluminoxane, and 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 deuterio-chloroform for compound No. 95 synthesized in Example 3, rac-dimethylsilylenebis[2-(2-furyl)-4,5-dimethyl-cyclopentadienyl]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-dimethyl-cyclopentadienyl]zirconium dichloride.

FIGS. 3A

,

3

B and

3

C represent three reaction steps in the synthesis of the metallocene compounds according to the present invention.

DETAILED DESCRIPTION

The metallocene compounds of the present invention represented by said formula (1) are largely classified into the compounds having a fundamental structure wherein Z is (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 substituted cycloalkadienyl group CA

1

is a substituted cyclopentadienyl group, a substituted indenyl group, a substituted tetrahydroindenyl group, a substituted benzoindenyl group or a substituted fluorenyl group, one or more hydrogens in the cycloalkadiene ring are substituted by the heteroaromatic group Ra and may be further substituted by the substituent R

1

.

Preferably, the heteroaromatic group Ra substitutes a hydrogen atom on the 5-membered ring in the substituted cycloalkadienyl group CA

1

, i.e., a hydrogen atom is substituted at a 2- and/or 3-position of the substituted cycloalkadienyl group CA

1

. Thus, preferable substituted cycloalkadienyl group CA

1

is a substituted cyclopentadienyl group, a substituted indenyl group, a substituted tetrahydroindenyl or benzoindenyl group, more preferably a substituted cyclopentadienyl group or a substituted indenyl group.

The number of substitution by the heteroaromatic group Ra on the substituted cycloalkadienyl group CA

1

: p 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 cyclopentadienyl group, an unsubstituted or substituted indenyl group, an unsubstituted or substituted tetrahydroindenyl group, an unsubstituted or substituted benzoindenyl group, or an unsubstituted or substituted fluorenyl group. These substituted cycloalkadienyl groups are those wherein one or more hydrogen atoms on the cycloalkadienyl ring 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, similarly to the substituted cycloalkadienyl group CA

1

.

The number of substitution by the heteroaromatic group Ra on CA

2

: q is 0 or an integer of 1 to 8, preferably 1 to 4, more preferably 1 or 2.

The heteroaromatic group Ra which substitutes a hydrogen atom on the respective cyclopentadienyl rings of CA

1

and CA

2

is the groups containing an oxygen atom, a sulfur atom or a nitrogen atom in the aromatic ring, e.g., furyl, thienyl, pyridyl, benzofliryl, benzothienyl, quinolyl, or pyrrolyl or indolyl having a bond at positions other than the 1-position, and those groups may be further substituted by the substituent R

1

as mentioned later. Where CA

1

and CA

2

are respectively substituted by Ra or plural Ra, said Ra may be identical or different.

Each of the substituents R

1

on CA

1

and CA

2

is a halogen atom such as fluorine, chlorine, bromine, iodine or the like; a hydrocarbon group of 1-20 carbons such as 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, an aralkyloxy group of 7-20 carbons or the like; 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; or a monocyclic or polycyclic amino group. Where CA

1

and CA

2

are respectively substituted by R

1

or plural R

1

, said R

1

may be identical or different.

The number of substitution by R

1

on CA

1

and CA

2

: each of m and n is 0 or an integer of 1 to 8, preferably 1 to 4, more preferably 1 or 2.

As the alkyl group of 1-20 carbons are recited, for example, a straight- or branched-chain alkyl group such as methyl, ethyl, propyl, i-propyl, n-butyl, i-butyl, tert-butyl, sec-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, dodecyl, octadecyl or the like, and a cyclic alkyl group which may be substituted by said chain alkyl group such as cyclopropyl, cycloheptyl, cyclohexyl or the like.

As the aryl group of 6-20 carbons are recited, for example, phenyl, naphthyl, anthryl or the like; and tolyl, xylyl, trimethylphenyl or the like which are further substituted by said alkyl group or the like. As the aralkyl group of 7-20 carbons are recited benzyl, naphthylmethyl, anthrylmethyl or the like; and (methylphenyl)methyl, (dimethylphenyl) methyl, (trimethylphenyl) methyl, (ethylphenyl)methyl, (propylphenyl)methyl, (butylphenyl)methyl or the like which are further substituted by said alkyl group or the like.

As the alkoxy group of 1-20 carbons are recited chain and cyclic alkoxy groups having said alkyl group, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, t-butoxy, hexyloxy, cyclohexyloxy or the like; as the aryloxy group of 6-20 carbons are recited substituted or unsubstituted aryloxy groups having said aryl group such as phenoxy, naphthyloxy, anthryloxy or the like; and as the aralkyloxy group of 7-20 carbons are recited aralkyloxy groups having said aralkyl group such as benzyloxy or the like.

As the halogenated hydrocarbon group are recited halogenated alkyl groups, halogenated aryl groups, halogenated aralkyl groups, halogenated alkoxy groups, halogenated aryloxy groups, halogenated aralkyloxy groups or the like wherein a part or all of the hydrogen atoms in said hydrocarbon group are substituted by said halogen atom, such as monochloromethyl, dichloromethyl, trichloromethyl, perfluoroethyl, monochlorophenyl, difluorophenyl, monochlorobenzyl or the like.

As the silyl group are recited silyl groups substituted by said hydrocarbon group and/or said halogenated hydrocarbon group, e.g., trimethylsilyl, triethylsilyl, triphenylsilyl, tribenzylsilyl, triethoxysilyl, dimethylphenoxysilyl or the like.

As the amino group are recited amino groups having said hydrocarbon group such as dimethylamino, diethylamino, methylethylamino or the like, and saturated or unsaturated monocyclic or polycyclic amino groups such as 1-pyrrolidyl, 1-pyrrolyl, 1-indolyl or the like.

The divalent linking group Y is —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; or —Sn(R

2

)

2

—, e.g., stanylene wherein the substituent R

2

is independently a hydrogen atom, a halogen atom, a hydrocarbon group of 1-20 carbons as defined above for the substituent R

1

, a halogenated hydrocarbon group or a silyl group.

Preferred linking group Y is —C(R

2

)

2

—, e.g., methylene, dichloromethylene, dimethylmethylene, diphenylmethylene, etc., —C

2

(R

2

)

4

—, e.g., ethylene, tetrachloroethylene, tetramethylethylene, tetraethylethylene, dimethyldiphenylethylene, etc., —Si (R

2

)

2

—, e.g., dichlorosilylene, dimethylsilylene, diethylsilylene, etc., and —Ge(R

2

)

2

—, e.g., dichlorogermanylene, dimethylgermanylene, etc.

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 said 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 includes a racemic form consisting of a stereostructurally unsymmetrical compound with respect to the plane containing M and its enantiomer, a meso form consisting of a stereostructurally symmetrical compound with respect to the plain 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, concrete examples of metallocene compounds represented by formula (2d) are shown in the attached Tables 10-13, concrete examples of metallocene compounds represented by formula (2e) are shown in the attached Tables 14-17 and concrete examples of metallocene compounds represented by formula (2g) are shown in the attached Tables 18 and 19, 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 2-19 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

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, a substituted benzoindenyl group and a substituted fluorenyl group.

The metallocene compounds of said 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 (5A), 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 said 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 said 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 said formula (1).

The compound represented by said formula (2A) can be prepared by reacting the substituted cycloalkadiene anion represented by said formula (4Aa) with the binding agent represented by said 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 said 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 said formula (5A) 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 said formula (5B) can produce the metallocene compounds of said 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 said formula (5d) by replacing OH with —SH.

The compounds represented by formula (Sf): 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.

As the binding agents represented by said formula (5A) are recited 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, dibromotetraethylethane or the like; 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, dibromodiphenylsilane or the like; 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, dibromogermaniumdiphenyl or the like; 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 said 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, hafnium tetrafluoride or the like; 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 reaction with a transition metal compound subsequent to dianionization.

As the metal salt type bases used in the anionization of the cyclopentadiene and aromatic rings in each step of the above-mentioned processes are recited, 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, t-butylmagnesium bromide or the like.

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, ethylenediamine or the like; secondary amines, e.g. dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-tert-butylamine, pyrrolidine, hexamethyldisilazane, diphenylamine or the like; 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, 4-dimethylaminopyridine or the like.

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 are preferable relatively low-molecular ethers such as diethylether, diisopropylether, tetrahydrofuran, dimethoxyethane or the like. Dichloromethane is preferable for halogenated hydrocarbons. For aromatic compounds are preferable 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 said formula (2A) is mentioned below.

The bis-substituted cycloalkadiene prepared by reacting the substituted cycloalkadiene anion represented by said 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. As the method of separating the bis-substituted cycloalkadiene from the solution can be employed, for example, the method wherein the solvent is distilled off. 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 said 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 dimethyl-silylenebis[2-(2-furyl)-3,5-dimethyl-cyclopentadienyl]-zirconium dichloride (Compound No. 94 in the attached Table 3), represented by said formula (2A) wherein CA

1

is a cyclopentadienyl ring 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 said formula (1) as a principal component. Preferably, the metallocene compounds represented by said formula (2), and more preferably, the metallocene compounds represented by said formula (2A) are used as the principal component.

The metallocene compounds represented by said 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, 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. As such anions are recited the anions of organoboron compounds, organoaluminum compounds or the like. As the cations are recited metallic cations, organometallic cations, carbonium cations, tropium cations, oxonium cations, sulfonium cations, phosphonium cations, ammonium cations or the like. Of these, preferable are ionic compounds containing a boron atom as an anion. In the concrete, there are recited N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, trityltetrakis-(pentafluorophenyl)borate or the like.

For Lewis acid is preferable a boron-containing Lewis acid. In the concrete, there are recited 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, tris(pentafluorophenyl)boron or the like.

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. As such supports are employed 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 are preferable metal oxides, e.g., SiO

2

, Al

2

O

3

, MgO, TiO

2

, ZnO or the like, 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

, SiO

2

—Al

2

O

3

—MgO or the like. 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 a-olefins of 2-12 carbons such as ethylene, propylene, 1-butene, 4-methyl-1-pentene or the like, 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. Thus, the term “olefin polymer” includes a homopolymer of one olefin and a copolymer of two or more olefins.

In the present invention, as the polymerizable olefins are recited straight-chain α-olefins such as ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene or the like, branched-chain α-olefins such as 3-methyl-1-butene, 4-methyl-1-pentene, 2-methyl-1-pentene or the like, 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.

As the polymerizable cyclic olefins are recited, for example, cyclobutene, cyclopentene, cyclohexene, cycloheptene, norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, phenylnorbornene, indanylnorbornene or the like. As the dienes are recited, for example, cyclic dienes such as 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-propylidene-5-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene or the like, and acyclic dienes such as 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, 1,9-decadiene or the like. As the styrenes and the derivatives thereof are recited, for example, styrene, p-chlorostyrene, p-methylstyrene, p-tert-butylstyrene, α-methylstyrene, vinylnaphthalene or the like. As other polymerizable monomers having a double bond are recited, for example, vinylcyclohexane, vinyl chloride, 4-trimethylsiloxy-1,6-heptadiene, 5-(N,N-diisopropylamino)-1-pentene, methylmethacrylate, ethylacrylate or the like.

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, a liquid 1-butene or the like can be used as a solvent. As the solvents for polymerization are recited an aromatic hydrocarbon such as benzene, toluene, ethylbenzene, xylene or the like, an aliphatic hydrocarbon such as butane, isobutane, pentane, hexane, heptane, octane, decane, dodecane, hexadecane, octadecane or the like, an alicyclic hydrocarbon such as cyclopentane, methylcyclopentane, cyclohexane, cyclooctane or the like and a petroleum cut such as gasoline, kerosene, gas oil or the like.

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 said polymerization process, particularly the metallocene compounds of said 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-dimethyl-cyclopentadienyl]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-dimethyl-cyclopenten-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 a 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-dimethylcyclopenta-diene. The structure was identified by NMR.

(a2) Synthesis of dimethylbis[3-(2-furyl)-2,5-dimethyl-cyclopentadienyl] 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 a 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-dimethyl-cyclopentadienyl] 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-dimethyl-cyclopentadienyl]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 (s, 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-dimethyl-cyclopentadienyl]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 dimethylsilylenebis[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-dimethyl-cyclopentadienyl]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-dimethyl-silylenebis[2-(2-furyl)-3,5-dimethyl-cyclopentadienyl]-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-dimethyl-cyclopentadienyl]zirconium dichloride (Compound No. 95)

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

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-dimethyl-cyclopenten-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 a 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-dimethyl-cyclopentadiene as a red liquid. The structure was identified by NMR.

(a2) Synthesis of dimethlbis[2-(2-furyl)-4,5-dimethyl-cyclopentadienyl] 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 dimethyl bis[2-(2-furyl)-4,5-dimethyl-cyclopentadienyl] silane as yellow crystals.

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

A 500 ml glass reaction vessel was charged with 10.0 g (0.027 mol) of dimethylbis[2-(2-furyl-)-4,5-dimethyl-cyclopentadienyl] 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-dimethyl-cyclopentadienyl]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-dimethyl-cyclopentadienyl]zirconium dichloride (Compound No. 274)

(a1) Synthesis of 1-(2-thienyl)-2,4-dimethyl-cyclopentadiene

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-dimethyl-cyclopenten-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-dimethyl-cyclopentadiene. The structure was identified by NMR.

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

A 100 ml glass reaction vessel was charged with 3.53 g (0.020 mol) of 1-(2-thienyl)-2,4-dimethyl-cyclopentadiene 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-dimethyl-cyclopentadienyl] silane. The structure was identified by NMR.

(b) Synthesis of dimethylsilylenebis[3-(2-thienyl)-2,5-dimethyl-cyclopentadienyl]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-dimethyl-cyclopentadienyl] 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-dimethyl-cyclopentadienyl)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 a 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)=101000, 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 0.30×10

−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 MPa 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, 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.

TABLE 1

Analytical Values for Polypropylene

Am-

Activ-

ount

ity

of Zr

kg-pp/

Metallocene

×10

−6

Yield

mmol

Mw

Mw/M

Tm

compound

mol

g

-M-h

×10

4

n

° C.

Mmmm

1

1.35

43.1

67

13.3

1.77

153.6

0.941

Me

2

Si

2

0.62

42.7

69

48.3

1.91

156.9

0.956

Me

2

Si(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-

Furyl-4,5-

Me

2

-Cp)

2

ZrCl

2

4

1.61

33.6

35

23.8

1.77

148.9

0.938

Me

2

Si(3-

Thienyl-3,5-

Me

2

-Cp)

2

ZrCl

2

5

0.30

4.6

15

128

2.30

148.0

0.925

Me

2

Si (3-

Furyl-3,5-

Me

2

-Cp)

2

ZrCl

2

TABLE 2

CA

1

: Cyclopentadiene

CA

2

: Cyclopentadiene

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(Me)

2

—

22

Zr

Cl

2-(2-Fu)

4-Me, 5-Me

3

2-(2-Fu)

4-Me, 5-Me

3

—C(Me)

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

: Cyclopentadiene

CA

2

: Cyclopentadiene

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

(Me)

4

—

62

Zr

Cl

2-(2-Fu)

4-Me, 5-Me

3

2-(2-Fu)

4-Me, 5-Me

3

—C

2

(Me)

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

: Cyclopentadiene

CA

2

: Cyclopentadiene

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(Me)

2

—

102

Zr

Cl

2-(2-Fu)

4-Me, 5-Me

3

2-(2-Fu)

4-Me, 5-Me

3

—Si(Me)

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

: Cyclopentadiene

CA

2

: Cyclopentadiene

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(Me)

2

—

142

Zr

Cl

2-(2-Fu)

4-Me, 5-Me

3

2-(2-Fu)

4-Me, 5-Me

3

—Ge(Me)

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

: Cyclopentadiene

CA

2

: Cyclopentadiene

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

—GeH

2

—

162

Zr

Cl

3-(2-Fu)

—

1

3-(2-Fu)

—

1

—Ge(Me)

2

—

163

Zr

Cl

3-(2-Fu)

5-Me

2

3-(2-Fu)

5-Me

2

—Ge(Me)

2

—

164

Zr

Cl

3-(2-Fu)

4-Me

2

3-(2-Fu)

4-Me

2

—Ge(Me)

2

—

165

Zr

Cl

3-(2-Fu)

4-OMe

2

3-(2-Fu)

4-OMe

2

—Ge(Me)

2

—

166

Zr

Cl

3-(2-Fu)

4-OPh

2

3-(2-Fu)

4-OPh

2

—Ge(Me)

2

—

167

Zr

Cl

3-(2-Fu)

4-Bzl

2

3-(2-Fu)

4-Bzl

2

—Ge(Me)

2

—

168

Zr

Cl

3-(2-Fu)

4-Tol

2

3-(2-Fu)

4-Tol

2

—Ge(Me)

2

—

169

Zr

Cl

3-(2-Fu)

4-OBzl

2

3-(2-Fu)

4-OBzl

2

—Ge(Me)

2

—

170

Zr

Cl

3-(2-Fu)

4-TMS

2

3-(2-Fu)

4-TMS

2

—Ge(Me)

2

—

171

Zr

Cl

3-(2-Fu)

4-(1-Pyr)

2

3-(2-Fu)

4-(1-Pyr)

2

—Ge(Me)

2

—

172

Zr

Cl

3-(2-Fu)

4-(1-Indo)

2

3-(2-Fu)

4-(1-Indo)

2

—Ge(Me)

2

—

173

Zr

Cl

3-(2-Fu)

2-Me

2

3-(2-Fu)

3-Me

2

—Ge(Me)

2

—

174

Zr

Cl

3-(2-Fu)

4-Me, 5-Me

3

3-(2-Fu)

3-Me, 5-Me

3

—Ge(Me)

2

—

175

Zr

Cl

3-(2-Fu)

4-Me, 5-Me

3

3-(2-Fu)

4-Me, 5-Me

3

—Ge(Me)

2

—

176

Zr

Cl

3-(2-Fu)

4-Et, 5-Me

3

3-(2-Fu)

4-Et, 5-Me

3

—Ge(Me)

2

—

177

Zr

Cl

3-(2-Fu)

4-(i-Pr), 5-Me

3

3-(2-Fu)

4-(i-Pr), 5-Me

3

—Ge(Me)

2

—

178

Zr

Cl

3-(2-Fu)

4-(t-Bu), 5-Me

3

3-(2-Fu)

4-(t-Bu), 5-Me

3

—Ge(Me)

2

—

179

Zr

Cl

3-(2-Fu)

4-Ph, 5-Me

3

3-(2-Fu)

4-Ph, 5-Me

3

—Ge(Me)

2

—

180

Zr

Cl

3-(2-Fu)

2-Ph, 5-Me

3

3-(2-Fu)

3-Ph, 5-Me

3

—Ge(Me)

2

—

181

Zr

Cl

3-(2-Fu)

4-Me, 5-Me

3

3-(2-Fu)

4-Me, 5-Me

3

—Ge(Me)

2

—

182

Zr

Cl

3-(2-Fu)

4-Me, 5-Me

3

3-(2-Fu)

4-Me, 5-Me

3

—Ge(Me)

2

—

183

Zr

Me

3-(2-Fu)

4-Me, 5-Me

3

3-(2-Fu)

4-Me, 5-Me

3

—Ge(Me)

2

—

184

Zr

Bzl

3-(2-Fu)

4-Me, 5-Me

3

3-(2-Fu)

4-Me, 5-Me

3

—Ge(Me)

2

—

185

Hf

Cl

3-(2-Fu)

4-Me, 5-Me

3

3-(2-Fu)

4-Me, 5-Me

3

—Ge(Me)

2

—

186

Ti

Cl

3-(2-Fu)

4-Me, 5-Me

3

3-(2-Fu)

4-Me, 5-Me

3

—Ge(Me)

2

—

187

Hf

Cl

3-(2-Fu)

2-Me, 5-Me

3

3-(2-Fu)

3-Me, 5-Me

3

—Ge(Me)

2

—

188

Ti

Cl

3-(2-Fu)

2-Me, 5-Me

3

3-(2-Fu)

3-Me, 5-Me

3

—Ge(Me)

2

—

189

Zr

Cl

3-(3-Fu)

4-Me, 5-Me

3

3-(3-Fu)

4-Me, 5-Me

3

—Ge(Me)

2

—

190

Zr

Cl

3-(3-Fu)

2-Me, 5-Me

3

3-(3-Fu)

3-Me, 5-Me

3

—Ge(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

—Ge(Me)

2

—

192

Zr

Cl

3-[2-(3-Me-Fu)]

2-Me, 5-Me

3

3-[2-(3-Me-Fu)]

3-Me, 5-Me

3

—Ge(Me)

2

—

193

Zr

Cl

3-(2-Thie)

4-Me, 5-Me

3

3-(2-Thie)

4-Me, 5-Me

3

—Ge(Me)

2

—

194

Zr

Cl

3-(2-Thie)

2-Me, 5-Me

3

3-(2-Thie)

3-Me, 5-Me

3

—Ge(Me)

2

—

195

Zr

Cl

3-(2-Py)

4-Me, 5-Me

3

3-(2-Py)

4-Me, 5-Me

3

—Ge(Me)

2

—

196

Zr

Cl

3-(2-Py)

2-Me, 5-Me

3

3-(2-Py)

3-Me, 5-Me

3

—Ge(Me)

2

—

197

Zr

Cl

3-(2-BzFu)

4-Me, 5-Me

3

3-(2-BzFu)

4-Me, 5-Me

3

—Ge(Me)

2

—

198

Zr

Cl

3-(2-BzFu)

2-Me, 5-Me

3

3-(2-BzFu)

3-Me, 5-Me

3

—Ge(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

—Ge(Me)

2

—

200

Zr

Cl

3-[2-(N-Me-Pyr)]

2-Me, 5-Me

3

3-[2-(N-Me-Pyr)]

3-Me, 5-Me

3

—Ge(Me)

2

—

TABLE 7

CA

1

: Cyclopentadiene

CA

2

: Cyclopentadiene

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

(Me)

4

—

222

Zr

Cl

3-(2-Fu)

4-Me, 5-Me

3

3-(2-Fu)

4-Me, 5-Me

3

—C

2

(Me)

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

: Cyclopentadiene

CA

2

: Cyclopentadiene

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(Me)

2

—

262

Zr

Cl

3-(2-Fu)

4-Me, 5-Me

3

3-(2-Fu)

4-Me, 5-Me

3

—Si(Me)

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

: Cyclopentadiene

CA

2

: Cyclopentadiene

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)

4-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(Me)

2

—

302

Zr

Cl

3-(2-Fu)

4-Me, 5-Me

3

3-(2-Fu)

4-Me, 5-Me

3

—Ge(Me)

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

: Cyclopentadiene

CA

2

: Cyclopentadiene

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)

5-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)

4-OMe

2

—C(Me)

2

—

326

Zr

Cl

2-(2-Fu)

3-Me, 7-Me

3

2-(2-Fu)

4-OPh

3

—C(Me)

2

—

327

Zr

Cl

2-(2-Fu)

4-Me, 7-Me

3

2-(2-Fu)

4-Bzl

3

—C(Me)

2

—

328

Zr

Cl

2-(2-Fu)

4-Cl

2

2-(2-Fu)

4-Tol

2

—C(Me)

2

—

329

Zr

Cl

2-(2-Fu)

4-Et

2

2-(2-Fu)

4-OBzl

2

—C(Me)

2

—

330

Zr

Cl

2-(2-Fu)

4-i-Pr

2

2-(2-Fu)

4-TMS

2

—C(Me)

2

—

331

Zr

Cl

2-(2-Fu)

4-t-Bu

2

2-(2-Fu)

4-(1-Pyr)

2

—C(Me)

2

—

332

Zr

Cl

2-(2-Fu)

4-Ph

2

2-(2-Fu)

4-(1-Indo)

2

—C(Me)

2

—

333

Zr

Cl

2-(2-Fu)

4-Np

2

2-(2-Fu)

2-Me

2

—C(Me)

2

—

334

Zr

Cl

2-(2-Fu)

4-OMe

2

2-(2-Fu)

2-Me, 5-Me

2

—C(Me)

2

—

335

Zr

Cl

2-(2-Fu)

4-OPh

2

2-(2-Fu)

4-Me, 5-Me

2

—C(Me)

2

—

336

Zr

Cl

2-(2-Fu)

4-Bzl

2

2-(2-Fu)

4-Et, 5-Me

2

—C(Me)

2

—

337

Zr

Cl

2-(2-Fu)

4-Tol

2

2-(2-Fu)

4-(i-Pr), 5-Me

2

—C(Me)

2

—

338

Zr

Cl

2-(2-Fu)

4-Obzl

2

2-(2-Fu)

4-(t-Bu), 5-Me

2

—C(Me)

2

—

339

Zr

Cl

2-(2-Fu)

4-TMS

2

2-(2-Fu)

4-Ph, 5-Me

2

—C(Me)

2

—

340

Zr

Cl

2-(2-Fu)

4-(1-Pyr)

2

2-(2-Fu)

2-Ph, 5-Me

2

—C(Me)

2

—

341

Zr

Cl

2-(2-Fu)

4-(1-Indo)

2

2-(2-Fu)

4-Me, 5-Me

2

—C(Me)

2

—

342

Zr

Cl

2-(2-Fu), 4-(2-Fu)

—

2

2-(2-Fu)

4-Me, 5-Me

2

—C(Me)

2

—

343

Zr

Me

2-(2-Fu), 4-(2-Thie)

—

2

2-(2-Fu)

4-Me, 5-Me

2

—C(Me)

2

—

344

Zr

Bzl

2-(2-Fu), 4-(2-BzFu)

—

2

2-(2-Fu)

4-Me, 5-Me

2

—C(Me)

2

—

345

Hf

Cl

2-(2-Fu), 4-(2-Py)

—

2

2-(2-Fu)

4-Me, 5-Me

2

—C(Me)

2

—

346

Ti

Cl

2-(2-Fu), 4-(1-MePyr)

—

2

2-(2-Fu)

4-Me, 5-Me

2

—C(Me)

2

—

347

Hf

Cl

2-(2-Fu)

4-Et, 7-Et

3

2-(2-Fu)

2-Me, 5-Me

3

—C(Me)

2

—

348

Ti

Cl

2-(2-Fu)

4-i-Pr, 7-i-Pr

3

2-(2-Fu)

2-Me, 5-Me

3

—C(Me)

2

—

349

Zr

Cl

2-(2-Fu)

4-t-Bu, 7-t-Bu

3

2-(2-Fu)

4-Me, 5-Me

3

—C(Me)

2

—

350

Zr

Cl

2-(2-Fu)

4-Ph, 7-Me

3

2-(2-Fu)

2-Me, 5-Me

3

—C(Me)

2

—

351

Zr

Cl

2-(2-Fu)

3-Ph, 7-Me

3

2-(2-Fu)

4-Me, 5-Me

3

—C(Me)

2

—

352

Zr

Cl

2-(2-Fu)

4-Me, 7-Me

3

2-(2-Fu)

2-Me, 5-Me

3

—C(Me)

2

—

353

Zr

Cl

2-(2-Fu)

4-Me, 7-Me

3

2-(2-Fu)

4-Me, 5-Me

3

—C(Me)

2

—

354

Zr

Cl

2-(2-Fu)

4-Ph

2

2-(2-Fu)

2-Me, 5-Me

2

—C(Me)

2

—

355

Zr

Cl

2-(2-Fu)

4-Ph

2

2-(2-Fu)

4-Me, 5-Me

2

—C(Me)

2

—

356

Zr

Cl

2-(2-Fu)

4-Ph

2

2-(2-Fu)

2-Me, 5-Me

2

—C(Me)

2

—

357

Zr

Cl

2-(2-Fu)

4-Ph

2

2-(2-Fu)

4-Me, 5-Me

2

—C(Me)

2

—

358

Zr

Cl

2-(2-Fu)

3-Me, 7-Me

3

2-(2-Fu)

2-Me, 5-Me

3

—C(Me)

2

—

359

Zr

Cl

2-(2-Fu)

3-Me, 7-Me

3

2-(2-Fu)

4-Me, 5-Me

3

—C(Me)

2

—

360

Zr

Cl

2-(3-Fu)

4-Ph

2

2-(3-Fu)

2-Me, 5-Me

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

: Cyclopentadiene

CA

2

: Cyclopentadiene

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

2

2-(2-Fu)

3-Me, 7-Me

3

—C

2

(Me)

4

—

378

Zr

Cl

2-(2-Fu)

4-Me, 7-Me

2

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)

2-Np

2

2-(2-Fu)

2-Np

2

—C

2

(Me)

4

—

385

Zr

Cl

2-(2-Fu)

2-OMe

2

2-(2-Fu)

2-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

Me

2-(2-Fu), 4-(2-Thie)

—

2

2-(2-Fu), 4-(2-Thie)

—

2

—C

2

(Me)

4

—

395

Zr

Bzl

2-(2-Fu), 4-(2-BzFu)

—

2

2-(2-Fu), 4-(2-BzFu)

—

2

—C

2

(Me)

4

—

396

Hf

Cl

2-(2-Fu), 4-(2-Py)

—

2

2-(2-Fu), 4-(2-Py)

—

2

—C

2

(Me)

4

—

397

Ti

Cl

2-(2-Fu), 4-(1-MePyr)

—

2

2-(2-Fu), 4-(1-MePyr)

—

2

—C

2

(Me)

4

—

398

Hf

Cl

2-(2-Fu)

4-Et, 7-Et

3

2-(2-Fu)

4-Et, 7-Et

3

—C

2

(Me)

4

—

399

Ti

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-(2-Fu)

4-Me, 7-Me

3

—C

2

(Me)

4

—

404

Zr

Cl

2-(2-Fu)

4-Me, 7-Me

3

2-(2-Fu)

4-Me, 7-Me

3

—C

2

(Me)

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-[(3-Me-Fu)]

4-Ph

2

2-[2-(3-Me-Fu)]

4-Ph

2

—C

2

(Me)

4

—

414

Zr

Cl

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-BsFu)

4-Ph

2

—C

2

(Me)

4

—

420

Zr

Cl

2-(2-BzFu)

—

1

2-(2-BsFu)

—

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

: Cyclopentadiene

CA

2

: Cyclopentadiene

No.

M

X

Ra

R

1

p + m

Ra

R

1

q + n

Y

423

Zr

Cl

2-(2-Fu)

—

1

3-(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

2

—Si(Me)

2

—

429

Zr

Cl

2-(2-Fu)

4-Me, 7-Me

3

2-(2-Fu)

3-Me, 7-Me

2

—Si(Me)

2

—

430

Zr

Cl

2-(2-Fu)

4-Cl

2

2-(2-Fu)

4-Me, 7-Me

2

—Si(Me)

2

—

431

Zr

Cl

2-(2-Fu)

4-Et

2

2-(2-Fu)

4-Cl

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

Me

2-(2-Fu), 4-(2-Thie)

—

2

2-(2-Fu), 4-(2-Thie)

—

2

—Si(Me)

2

—

446

Zr

Bzl

2-(2-Fu), 4-(2-BzFu)

—

2

2-(2-Fu), 4-(2-BzFu)

—

2

—Si(Me)

2

—

447

Hf

Cl

2-(2-Fu), 4-(2-Py)

—

2

2-(2-Fu), 4-(2-Py)

—

2

—Si(Me)

2

—

448

Ti

Cl

2-(2-Fu), 4-(1-MePyr)

—

2

2-(2-Fu), 4-(1-MePyr)

—

2

—Si(Me)

2

—

449

Hf

Cl

2-(2-Fu)

4-Et, 7-Et

3

2-(2-Fu)

4-Et, 7-Et

3

—Si(Me)

2

—

450

Ti

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(Me)

2

—

455

Zr

Cl

2-(2-Fu)

4-Me, 7-Me

3

2-(2-Fu)

4-Me, 7-Me

2

—Si(Me)

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

: Cyclopentadiene

CA

2

: Cyclopentadiene

No.

M

X

Ra

R

1

p + m

Ra

R

1

q + n

Y

474

Zr

Cl

2-(2-Fu)

—

1

3-(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

2

—Ge(Me)

2

—

480

Zr

Cl

2-(2-Fu)

4-Me, 7-Me

3

2-(2-Fu)

3-Me, 7-Me

2

—Ge(Me)

2

—

481

Zr

Cl

2-(2-Fu)

4-Cl

2

2-(2-Fu)

4-Me, 7-Me

2

—Ge(Me)

2

—

482

Zr

Cl

2-(2-Fu)

4-Et

2

2-(2-Fu)

4-Cl

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

Me

2-(2-Fu), 4-(2-Thie)

—

2

2-(2-Fu), 4-(2-Thie)

—

2

—Ge(Me)

2

—

497

Zr

Bzl

2-(2-Fu), 4-(2-BzFu)

—

2

2-(2-Fu), 4-(2-BzFu)

—

2

—Ge(Me)

2

—

498

Hf

Cl

2-(2-Fu), 4-(2-Py)

—

2

2-(2-Fu), 4-(2-Py)

—

2

—Ge(Me)

2

—

499

Ti

Cl

2-(2-Fu), 4-(1-MePyr)

—

2

2-(2-Fu), 4-(1-MePyr)

—

2

—Ge(Me)

2

—

500

Hf

Cl

2-(2-Fu)

4-Et, 7-Et

3

2-(2-Fu)

4-Et, 7-Et

3

—Ge(Me)

2

—

501

Ti

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(Me)

2

—

506

Zr

Cl

2-(2-Fu)

4-Me, 7-Me

3

2-(2-Fu)

4-Me, 7-Me

2

—Ge(Me)

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

: Cyclopentadiene

CA

2

: Cyclopentadiene

No.

M

X

Ra

R

1

p + m

Ra

R

1

q + n

Y

525

Zr

Cl

2-(2-Fu)

—

1

3-(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

2

—C(Me)

2

—

531

Zr

Cl

2-(2-Fu)

4-Me, 7-Me

3

2-(2-Fu)

3-Me, 7-Me

2

—C(Me)

2

—

532

Zr

Cl

2-(2-Fu)

4-Cl

2

2-(2-Fu)

4-Me, 7-Me

2

—C(Me)

2

—

533

Zr

Cl

2-(2-Fu)

4-Et

2

2-(2-Fu)

4-Cl

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

Me

2-(2-Fu), 4-(2-Thie)

—

2

2-(2-Fu), 4-(2-Thie)

—

2

—C(Me)

2

—

548

Zr

Bzl

2-(2-Fu), 4-(2-BzFu)

—

2

2-(2-Fu), 4-(2-BzFu)

—

2

—C(Me)

2

—

549

Hf

Cl

2-(2-Fu), 4-(2-Py)

—

2

2-(2-Fu), 4-(2-Py)

—

2

—C(Me)

2

—

550

Ti

Cl

2-(2-Fu), 4-(1-MePyr)

—

2

2-(2-Fu), 4-(1-MePyr)

—

2

—C(Me)

2

—

551

Hf

Cl

2-(2-Fu)

4-Et, 7-Et

3

2-(2-Fu)

4-Et, 7-Et

3

—C(Me)

2

—

552

Ti

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(Me)

2

—

557

Zr

Cl

2-(2-Fu)

4-Me, 7-Me

3

2-(2-Fu)

4-Me, 7-Me

2

—C(Me)

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

—

552

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

: Cyclopentadiene

CA

2

: Cyclopentadiene

No.

M

X

Ra

R

1

p + m

Ra

R

1

q + n

Y

576

Zr

Cl

2-(2-Fu)

—

1

3-(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

2

—C

2

(Me)

4

—

582

Zr

Cl

2-(2-Fu)

4-Me, 7-Me

3

2-(2-Fu)

3-Me, 7-Me

2

—C

2

(Me)

4

—

583

Zr

Cl

2-(2-Fu)

4-Cl

2

2-(2-Fu)

4-Me, 7-Me

2

—C

2

(Me)

4

—

584

Zr

Cl

2-(2-Fu)

4-Et

2

2-(2-Fu)

4-Cl

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

Me

2-(2-Fu), 4-(2-Thie)

—

2

2-(2-Fu), 4-(2-Thie)

—

2

—C

2

(Me)

4

—

599

Zr

Bzl

2-(2-Fu), 4-(2-BzFu)

—

2

2-(2-Fu), 4-(2-BzFu)

—

2

—C

2

(Me)

4

—

600

Hf

Cl

2-(2-Fu), 4-(2-Py)

—

2

2-(2-Fu), 4-(2-Py)

—

2

—C

2

(Me)

4

—

601

Ti

Cl

2-(2-Fu), 4-(1-MePyr)

—

2

2-(2-Fu), 4-(1-MePyr)

—

2

—C

2

(Me)

4

—

602

Hf

Cl

2-(2-Fu)

4-Et, 7-Et

3

2-(2-Fu)

4-Et, 7-Et

3

—C

2

(Me)

4

—

603

Ti

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

(Me)

4

—

608

Zr

Cl

2-(2-Fu)

4-Me, 7-Me

3

2-(2-Fu)

4-Me, 7-Me

2

—C

2

(Me)

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-(1-Me-Pyr)]

4-Ph

2

—C

2

(Me)

4

—

626

Zr

Cl

2-[2-(N-Me-Pyr)]

—

1

2-[2-(1-Me-Pyr)]

—

1

—C

2

(Me)

4

—

TABLE 16

CA

1

: Cyclopentadiene

CA

2

: Cyclopentadiene

No.

M

X

Ra

R

1

p + m

Ra

R

1

q + n

Y

627

Zr

Cl

2-(2-Fu)

—

1

3-(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

Me

2-(2-Fu), 4-(2-Thie)

—

2

2-(2-Fu), 4-(2-Thie)

—

2

—Si(Me)

2

—

650

Zr

Bzl

2-(2-Fu), 4-(2-BzFu)

—

2

2-(2-Fu), 4-(2-BzFu)

—

2

—Si(Me)

2

—

651

Hf

Cl

2-(2-Fu), 4-(2-Py)

—

2

2-(2-Fu), 4-(2-Py)

—

2

—Si(Me)

2

—

652

Ti

Cl

2-(2-Fu), 4-(1-MePyr)

—

2

2-(2-Fu), 4-(1-MePyr)

—

2

—Si(Me)

2

—

653

Hf

Cl

2-(2-Fu)

4-Et, 7-Et

3

2-(2-Fu)

4-Et, 7-Et

3

—Si(Me)

2

—

654

Ti

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(Me)

2

—

659

Zr

Cl

2-(2-Fu)

4-Me, 7-Me

3

2-(2-Fu)

4-Me, 7-Me

2

—Si(Me)

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

: Cyclopentadiene

CA

2

: Cyclopentadiene

No.

M

X

Ra

R

1

p + m

Ra

R

1

q + n

Y

678

Zr

Cl

2-(2-Fu)

—

1

3-(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

Me

2-(2-Fu), 4-(2-Thie)

—

2

2-(2-Fu), 4-(2-Thie)

—

2

—Ge(Me)

2

—

701

Zr

Bzl

2-(2-Fu), 4-(2-BzFu)

—

2

2-(2-Fu), 4-(2-BzFu)

—

2

—Ge(Me)

2

—

702

Hf

Cl

2-(2-Fu), 4-(2-Py)

—

2

2-(2-Fu), 4-(2-Py)

—

2

—Ge(Me)

2

—

703

Ti

Cl

2-(2-Fu), 4-(1-MePyr)

—

2

2-(2-Fu), 4-(1-MePyr)

—

2

—Ge(Me)

2

—

704

Hf

Cl

2-(2-Fu)

4-Et, 7-Et

3

2-(2-Fu)

4-Et, 7-Et

3

—Ge(Me)

2

—

705

Ti

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(Me)

2

—

710

Zr

Cl

2-(2-Fu)

4-Me, 7-Me

3

2-(2-Fu)

4-Me, 7-Me

2

—Ge(Me)

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

: Cyclopentadiene

CA

2

: Cyclopentadiene

No.

M

X

Ra

R

1

p + m

Ra

R

1

q + n

Y

729

Zr

Cl

2-(2-Fu)

—

1

3-(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

Me

2-(2-Fu), 5-(2-Thie)

—

2

2-(2-Fu), 5-(2-Thie)

—

2

—Si(Me)

2

—

752

Zr

Bzl

2-(2-Fu), 5-(2-BzFu)

—

2

2-(2-Fu), 5-(2-BzFu)

—

2

—Si(Me)

2

—

753

Hf

Cl

2-(2-Fu), 5-(2-Py)

—

2

2-(2-Fu), 5-(2-Py)

—

2

—Si(Me)

2

—

754

Ti

Cl

2-(2-Fu), 5-[2-(1-MePyr)

—

2

2-(2-Fu), 5-(1-MePyr)

—

2

—Si(Me)

2

—

755

Hf

Cl

2-(2-Fu)

5-Et, 9-Et

3

2-(2-Fu)

4-Et, 7-Et

3

—Si(Me)

2

—

756

Ti

Cl

2-(2-Fu)

5-i-Pr, 9-i-Pr

3

2-(2-Fu)

4-I-Pr, 7-I-Pr

3

—Si(Me)

2

—

757

Zr

Cl

2-(2-Fu)

5-t-Bu, 9-t-Bu

3

2-(2-Fu)

4-t-Bu, 7-t-Bu

3

—Si(Me)

2

—

758

Zr

Cl

2-(2-Fu)

5-Ph, 9-Ph

3

2-(2-Fu)

4-Ph, 7-Ph

3

—Si(Me)

2

—

759

Zr

Cl

2-(2-Fu)

5-Ph, 9-Me

3

2-(2-Fu)

3-Ph, 7-Me

3

—Si(Me)

2

—

760

Zr

Cl

2-(2-Fu)

5-Me, 9-Me

3

2-(2-Fu)

4-Me, 7-Me

3

—Si(Me)

2

—

761

Zr

Cl

2-(2-Fu)

5-Me, 9-Me

3

2-(2-Fu)

4-Me, 7-Me

2

—Si(Me)

2

—

762

Zr

Me

2-(2-Fu)

5-Ph

2

2-(2-Fu)

4-Ph

2

—Si(Me)

2

—

763

Zr

Bzl

2-(2-Fu)

5-Ph

2

2-(2-Fu)

4-Ph

2

—Si(Me)

2

—

764

Hf

Cl

2-(2-Fu)

5-Ph

2

2-(2-Fu)

4-Ph

2

—Si(Me)

2

—

765

Ti

Cl

2-(2-Fu)

5-Ph

2

2-(2-Fu)

4-Ph

2

—Si(Me)

2

—

766

Hf

Cl

2-(2-Fu)

3-Me, 9-Me

3

2-(2-Fu)

3-Me, 7-Me

3

—Si(Me)

2

—

767

Ti

Cl

2-(2-Fu)

3-Me, 9-Me

3

2-(2-Fu)

3-Me, 7-Me

3

—Si(Me)

2

—

768

Zr

Cl

2-(3-Fu)

5-Ph

2

2-(3-Fu)

4-Ph

2

—Si(Me)

2

—

769

Zr

Cl

2-(3-Fu)

5-Ph

2

2-(3-Fu)

4-Ph

2

—Si(Me)

2

—

770

Zr

Cl

2-[2-(3-Me-Fu)]

5-Ph

2

2-[2-(3-Me—Fu)]

4-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)

4-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)

4-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)

4-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)]

4-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

: Cyclopentadiene

CA

2

: Cyclopentadiene

No.

M

X

Ra

R

1

p + m

Ra

R

1

q + n

Y

780

Zr

Cl

2-(2-Fu)

—

1

3-(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

Me

2-(2-Fu), 5-(2-Thie)

—

2

2-(2-Fu), 5-(2-Thie)

—

2

—Ge(Me)

2

—

803

Zr

Bzl

2-(2-Fu), 5-(2-BzFu)

—

2

2-(2-Fu), 5-(2-BzFu)

—

2

—Ge(Me)

2

—

804

Hf

Cl

2-(2-Fu), 5-(2-Py)

—

2

2-(2-Fu), 5-(2-Py)

—

2

—Ge(Me)

2

—

805

Ti

Cl

2-(2-Fu), 5-[2-(1-MePyr)

—

2

2-(2-Fu), 5-[2-(1-MePyr)

—

2

—Ge(Me)

2

—

806

Hf

Cl

2-(2-Fu)

5-Et, 9-Et

3

2-(2-Fu)

5-Et, 9-Et

3

—Ge(Me)

2

—

807

Ti

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)

5-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(Me)

2

—

812

Zr

Cl

2-(2-Fu)

5-Me, 9-Me

3

2-(2-Fu)

5-Me, 9-Me

2

—Ge(Me)

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

: Cyclopentadiene

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(Me)

2

—

853

Ti

Cl

2-(2-Fu)

4-Me, 5-Me

3

Me

—Si(Me)

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

Me

2-(2-Fu)

3-Me, 5-Me

3

t-Bu

—Si(Me)

2

—

863

Zr

Bzl

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

Me

2-(2-BzFu)

3-Me, 5-Me

3

Me

—Si(Me)

2

—

874

Ti

Bzl

2-[2-(1-Me—Pyr)]

4-Me, 5-Me

3

t-Bu

—Si(Me)

2

—

875

Ti

Cl

2-[2-(1-Me—Fu)]

3-Me, 5-Me

3

Me

—Si(Me)

2

—

TABLE 21

CA

1

: Cyclopentadiene

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-Fti)

—

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-Fti)

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

—

Number	Name	Date	Kind
5585509	Langhauser et al.	Dec 1996
5840947	Kuber et al.	Nov 1998

Number	Date	Country
7-258282	Oct 1995	JP
8-183814	Jul 1996	JP

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

Information

Patent Number

Date Filed

Date Issued

Inventors

Original Assignees

Examiners

Agents

CPC

US Classifications

Field of Search

US

International Classifications

Abstract

Description

Claims

US Referenced Citations (2)

Foreign Referenced Citations (2)

Non-Patent Literature Citations (2)

Entry
“Elastomeric Polypropylene from Unbridged 2-Arylindenyl Zirconocenes: Modeling Polymerization Behavior Using ansa-Metallocene Analogues”, J. Am. Chem. Soc. 1998, vol. 120, pp. 11316-11322.
“Polymerization Catalysts with Cyclopentadienyl Ligands Ring-Fused to Pyrrole and Thiophene Heterocycles”, J. Am. Chem. Soc. 1998, vol. 120, pp. 10786-10787.