Substituted indenyl metal complexes and polymerization process

1. A metal compound corresponding to the formula:

CpM(Z) z (X) x (T) t (X′) x   (I),

Cp is a substituted inden-1-yl or partially hydrogenated derivative thereof substituted at least at the 2-position thereof with a C 4-30 alkyl, aralkyl, or trihydrocarbylsilylhydrocarbyl group, or a Group 15 or 16 heteroatom containing group corresponding to the formula:

wherein R 7 is hydrogen or C 1-10 alkyl,

said group containing 2 or 3 non-hydrogen substituents on at least one β-position thereof;

M is a metal selected from Groups 3–10 or the Lanthanide series of the Periodic Table of the Elements;

Z is a divalent moiety of the formula -Z′Y— joining Cp and M, wherein,

Y is —O—, —S—, —NR 5 —, —PR 5 , —NR 5 2 , or —PR 5 2 ;

Z′ is SiR 6 2 , CR 6 2 , SiR 6 2 SiR 6 2 , CR 6 2 CR 6 2 , CR 6 ═CR 6 , CR 6 2 SiR 6 2 , BR 6 , or GeR 6 2 , bound at the 1-position of Cp;

R 5 , independently each occurrence, is hydrocarbyl, trihydrocarbylsilyl, or trihydrocarbylsilylhydrocarbyl, said R 5 having up to 20 atoms other than hydrogen, and optionally two R 5 groups or R 5 together with Y form a ring system;

R 6 , independently each occurrence, is hydrogen, or a member selected from hydrocarbyl, hydrocarbyloxy, silyl, halogenated alkyl, halogenated aryl, —NR 5 2 , and combinations thereof, said R 6 having up to 30 non-hydrogen atoms, and optionally, two R 6 groups form a ring system;

X is hydrogen or a monovalent anionic ligand group having up to 60 atoms not counting hydrogen;

T independently each occurrence is a neutral ligating compound having up to 20 atoms, other than hydrogen, and optionally T and X are bonded together;

X′ is a divalent anionic ligand group having up to 60 atoms other than hydrogen;

z is 0, 1 or2;

x is 0, 1, 2, or3;

t is a number from 0 to 2, and

x′ is 0 or 1.

2. A metal compound according to claim 1 corresponding to the formula:

wherein:

R′ independently each occurrence is hydrogen, hydrocarbyl, trihydrocarbylsilyl, trihydrocarbylgermyl, halide, hydrocarbyloxy, trihydrocarbylsiloxy, bis(trihydrocarbylsilyl)amino, di(hydrocarbyl)amino, hydrocarbyleneamino, hydrocarbylimino, di(hydrocarbyl)phosphino, hydrocarbylenephosphino, hydrocarbylsulfido, halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, trihydrocarbylsilyl-substituted hydrocarbyl, trihydrocarbylsiloxy-substituted hydrocarbyl, bis(trihydrocarbylsilyl)amino-substituted hydrocarbyl, di(hydrocarbyl)amino-substituted hydrocarbyl, hydrocarbyleneanilno-substituted hydrocarbyl, di(hydrocarbyl)phosphino-substituted hydrocarbyl, hydrocarbylenephosphino-substituted hydrocarbyl, or hydrocarbylsulfido-substituted hydrocarbyl, said R′ group having up to 40 atoms not counting hydrogen atoms, and two R′ groups together may form a divalent derivative thereby forming a saturated or unsaturated ring;

R is a C 4-12 alkyl, aralkyl, or trihydrocarbylsilylhydrocarbyl group, or a Group 15 or 16 heteroatom containing group corresponding to the formula:

wherein R 7 is hydrogen or C 1-10 alkyl,

said R group containing 2 or 3 non-hydrogen substituents at the β-position thereof;

M is a Group 4 metal;

Z is -Z′-Y—;

Y is —O—, —S—, —NR 5 —, —PR 5 , —NR 5 2 , or —PR 5 2 ;

Z′ is SiR 6 2 , CR 6 2 , SiR 6 2 SiR 6 2 , CR 6 2 CR 6 2 , CR 6 ═CR 6 , CR 6 2 SiR 6 2 , BR 6 , or GeR 6 2 ;

R 5 each occurrence is independently hydrocarbyl, trihydrocarbylsilyl, or trihydrocarbylsilyihydrocarbyl, said R 5 having up to 20 atoms other than hydrogen, and optionally two R 5 groups or R 5 together with Y form a ring system;

R 6 each occurrence is independently hydrogen, or a member selected from hydrocarbyl, hydrocarbyloxy, silyl, halogenated ailcyl, halogenated aryl, —NR 5 2 , and combinations thereof, said R 6 having up to 20 non-hydrogen atoms, and optionally, two R 6 groups form a ring system;

X, T, and X′ are as previously defined in claim 1 ;

x is 0, 1 or 2;

t is 0 or 1; and

x′ is 0 or 1.

3. A metal compound according to claim 1 , corresponding to the formula:

wherein

M is titanium;

R is 2,2-dimethylpropan-1-yl, 2-methyl-2-phenylpropan-1-yl, benzyl, or parafluorophenylmethyl;

Y is —O—, —S—, —NR 5 —, —PR 5 , —NR 5 2 , or —PR 5 2 ;

Z′ is SiR 6 2 , CR 6 2 , SiR 6 2 SiR 6 2 , CR 6 2 CR 6 2 , CR 6 ═CR 6 , CR 6 2 SiR 6 2 , BR 6 , or GeR 6 2 ;

R 5 each occurrence is independently hydrocarbyl, trihydrocarbylsilyl, or trihydrocarbylsilylhydrocarbyl, said R 5 having up to 20 atoms other than hydrogen, and optionally two R 5 groups or R 5 together with Y form a ring system;

R 6 each occurrence is independently hydrogen, or a member selected from hydrocarbyl, hydrocarbyloxy, silyl, halogenated alkyl, halogenated aryl, —NR 5 2 , and combinations thereof, said

R 6 having up to 20 non-hydrogen atoms, and optionally, two R 6 groups form a ring system;

X, T, and X′ are as previously defined in claim 1 ;

x is 0, 1 or 2;

t is 0 or 1; and

x′ is 0 or 1;

and, when x is 2, x′ is zero, M is in the +4 formal oxidation state or M is in the +3 formal oxidation state if Y is —NR 5 2 or —PR 5 2 , and X is an anionic ligand selected from the group consisting of halide, hydrocarbyl, hydrocarbyloxy, di(hydrocarbyl)amido, di(hydrocarbyl)phosphido, hydrocarbylsulfido, and silyl groups, as well as halo-, di(hydrocarbyl)amino-, hydrocarbyloxy-, and di(hydrocarbyl)phosphino-Substituted derivatives thereof, said X group having up to 30 atoms not counting hydrogen,

when x is 0 and x′ is 1, M is in the +4 formal oxidation state, and X′ is a dianionic ligand selected from the group consisting of hydrocarbadiyl, oxyhydrocarbylene, and hydrocarbylenedioxy groups, said X′ group having up to 30 nonhydrogen atoms,

when x is 1, and x′ is 0, M is in the +3 formal oxidation state, and X is a stabilizing anionic ligand group selected from the group consisting of allyl, 2-(N,N-dimethylamino)phenyl, 2-(N,N-dimethylaminomethyl)phenyl, and 2-(N,N-dimethylamino)benzyl, and

when x and x′ are both 0, t is 1, M is in the +2 formal oxidation state, and T is a neutral, conjugated or nonconjugated diene, optionally substituted with one or more hydrocarbyl groups, said T having up to 40 carbon atoms and being bound to M by means of delocalized π-electrons thereof.

4. A metal complex according to claim 1 selected from the group consisting of:

(2-neopentylinden-1-yl)-N-( 1,1-dimethylethyl)dimethylsilanamide titanium (IV) dimethylenedimethylsilane,

(2-neopentylinden-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide titanium (II) 1,3-pentadiene,

(2-neopentylinden-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide titanium (III) 2-(N,N-dimethylamino)benzyl,

(2-neopentylinden-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide titanium (IV) dichioride,

(2-neopentylinden-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide titanium (IV) dimethyl,

(2-neopentylinden-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide titanium (IV) dibenzyl,

(2-(parafluorophenylmethyl)inden-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide titanium (IV) dimethylenedimethylsilane,

(2-(parafluorophenylmethyl)inden-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide titanium (II) 1,3-pentadiene,

(2-(parafluorophenylmethyl)inden-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide titanium (III) 2-(N,N-dimethylamino)benzyl,

(2-(parafluorophenylmethyl)inden-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide titanium (IV) dichioride,

(2-(parafluorophenylmethyl)inden-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide titanium (IV) dimethyl,

(2-(parafluorophenylmethyl)inden-1-yl)-N-(1,1-dimethylethyl)dimethylsilananude titanium (IV) dibenzyl,

(2-beuzylinden-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide titanium (IV) dimethylenedimethylsilane,

(2-benzylinden-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide titanium (II) 1,3-pentadiene,

(2-benzylinden-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide titanium (III) 2-(N,N-dimethylamino)benzyl,

(2-benzylinden-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide titanium (IV) dichioride,

(2-benzylinden-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide titanium (IV) dimethyl,

(2-benzylinden-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide titanium (IV) dibenzyl,

(2-(2,2-dimethyl-1-butylinden-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide titanium (IV) dimethylenedimethylsilane,

(2-(2,2-dimethyl-1-butylinden-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide titanium (II) 1,3-pentadiene,

(2-(2,2-dimethyl-1-butylinden-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide titanium (III) 2-(N,N-dimethylamino)benzyl,

(2-(2,2-dimethyl-1-butylinden-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide titanium (IV) dichioride,

(2-(2,2-dimethyl-1-butylinden-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide titanium (IV) dimethyl,

(2-(2,2-dimethyl-1-butylinden-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide titanium (IV) dibenzyl, and mixtures thereof.

5. An olefin polymerization process comprising contacting one or more olefin monomers under polymerization conditions with a catalyst composition comprising a metal complex according to any one of claims 1 – 4 .

6. The process of claim 5 wherein the catalyst composition additionally comprises an activating cocatalyst.

7. The process of claim 5 conducted under solution, slurry or high pressure polymerization conditions.

8. The process of claim 5 conducted under slurry or gas phase polymerization conditions, wherein the catalyst additionally comprises an inert, particulated support.

9. The process of claim 6 wherein the activating cocatalyst is: trispentafluorophenylborane, methylditetradecylanimonium tetrakis(pentafluorophenyl)borate, (pentafluorophenyl)ditetradecylammoflium tetrakis(pentafluorophenyl)borate, dimethyltetradecylammonium tetrakis(pentafluorophenyl)borate, methyldihexadecyl-animonium tetrakis(pentafluorophenyl)borate, (pentafluorophenyl)dihexadecylammonium tetrakis(pentafluorophenyl)borate, dimethylhexadecylammonium tetrakis(pentafluorophenyl)-borate, methyldioctadecylammonium tetrakis(pentafluorophenyl)borate, (pentafluorophenyl)dioctadecylammomum tetrakis(pentafluorophenyl)borate, dimethyloctadecylammonium tetrakis(pentafluorophenyl)borate, methylalumoxane, triisobutylaluminum modified methylalumoxane, or a mixture thereof.