CA2411712A1 - Polycyclic, fused ring compounds, metal complexes and polymerization process - Google Patents

Polycyclic, fused ring compounds, metal complexes and polymerization process Download PDF

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CA2411712A1
CA2411712A1 CA002411712A CA2411712A CA2411712A1 CA 2411712 A1 CA2411712 A1 CA 2411712A1 CA 002411712 A CA002411712 A CA 002411712A CA 2411712 A CA2411712 A CA 2411712A CA 2411712 A1 CA2411712 A1 CA 2411712A1
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hydrocarbyl
substituted hydrocarbyl
dimethyl
dihydrodibenzo
azulen
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CA2411712C (en
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Richard E. Campbell, Jr.
Jerzy Klosin
Ravi B. Shankar
Francis J. Timmers
Robert K. Rosen
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Dow Global Technologies LLC
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
    • C07C13/62—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with more than three condensed rings
    • C07C13/66—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with more than three condensed rings the condensed ring system contains only four rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
    • C07C2602/14—All rings being cycloaliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2420/00—Metallocene catalysts
    • C08F2420/02—Cp or analog bridged to a non-Cp X anionic donor
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2420/00—Metallocene catalysts
    • C08F2420/05—Cp or analog where at least one of the carbon atoms of the coordinating ring is replaced by a heteroatom
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/943—Polymerization with metallocene catalysts

Abstract

Compounds and metal complexes comprising a polycyclic, fused ring ligand or inertly substituted derivative thereof having up to 60 atoms other than hydrogen, said ligand comprising at least: (1) a cyclopentadienyl ring, (2) a 6,7, or 8 membered ring other than a 6-carbon aromatic ring, and (3) an aromatic ring, with the proviso that said 6, 7, or 8 membered ring (2), is fused to both the cyclopentadienyl ring (1), and the aromatic ring (3), polymerization catalysts, a process to prepare the novel compounds and complexes, and olefin polymerization processes using the same are disclosed.

Claims (13)

1. A polycyclic, fused ring compound corresponding to the formula:
(Cp*)p-M* (I) or CpM(Z)z(X)x(L)1(X')x' (II), where Cp* is a polycyclic, fused ring ligand or inertly substituted derivative thereof comprising at least: (1) a cyclopentadienyl ring, (2) a 6,7,or 8 membered ring other than a 6-carbon aromatic ring, and (3) an aromatic ring, with the proviso that said 6, 7, or 8 membered ring (2), is fused to both the cyclopentadienyl ring (1), and the aromatic ring (3), said Cp* having up to 60 atoms other than hydrogen;
p is 1 or 2;
when p is 1, M* is hydrogen, an alkali metal or an alkaline earth metal halide, and, when p is 2, M* is an alkaline earth metal; said M* being bound to at least one of the non-fused, ring-carbons of the cyclopentadienyl ring, (1);
Cp is the aromatic ligand group derived from Cp* by removal of M*;
M is a metal selected from Groups 3-10 or the Lanthanide series of the Periodic Table of the Elements;
Z is either:
a) a cyclic ligand group containing delocalized .pi.-electrons, including a second or third, fused, polycyclic ligand, Cp, said Z being bonded to M by means of delocalized .pi.-electrons and optionally also covalently bonded to Cp through a divalent bridging group, Z', or b) a divalent moiety of the formula -Z'Y-, wherein, Z' is SiR6 2, CR6 2, SiR6 2,SiR6 2, CR6 2CR6 2, CR6=CR6, CR6 2SiR6 2, BR6, BR6L", or GeR6 2;
Y is -O-, -S-, -NR5-, -PR5-; -NR5 2, or -PR5 2;
R5, independently each occurrence, is hydrocarbyl, trihydrocarbylsilyl, or trihydrocarbylsilylhydrocarbyl, said R5 having up to 20 atoms other than hydrogen, and optionally two R5 groups or R5 together with Y form a ring system;
R6, independently each occurrence, is hydrogen, or a member selected from hydrocarbyl, hydrocarbyloxy, silyl, halogenated alkyl, halogenated aryl, -NR5 2, and combinations thereof, said R6 having up to 20 non-hydrogen atoms, and optionally, two R6 groups form a ring system;
L" is a monodentate or polydentate Lewis base optionally bonded to R6;
X is hydrogen or a monovalent anionic ligand group having up to 60 atoms not counting hydrogen;
L independently each occurrence is a neutral ligating compound having up to 20 atoms, other than hydrogen, and optionally L and X are bonded together;
X' is a divalent anionic ligand group having up to 60 atoms other than hydrogen;
z is 0, 1 or 2;

x is 0,1,2,or3;
1 is a number from 0 to 2, and x'is 0 or 1.
2. A compound or complex according to claim 1 corresponding to the formula:
structural isomers thereof wherein one or more double bonds occupy different positions within the various rings, and mixtures thereof, wherein:

T independently each occurrence is carbon, silicon, nitrogen, phosphorus, oxygen, sulfur, or boron;
J 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, hydrocarbyleneamino-substituted hydrocarbyl, di(hydrocarbyl)phosphino- substituted hydrocarbyl, hydrocarbylenephosphino-substituted hydrocarbyl, or hydrocarbylsulfido- substituted hydrocarbyl, said J group having up to 40 atoms not counting hydrogen atoms, and optionally two J groups together form a divalent derivative thereby forming a saturated or unsaturated ring, with the proviso that, in at least one occurrence, two or more of the foregoing J groups on different atoms, at least one or which is T, together form a divalent derivative, thereby forming at least one aromatic ring that is fused to the 6, 7, or 8 membered ring;
t is 0, 1 or 2; and, for compounds of formula (1A1) or (1A2) where T is carbon, in at least one occurrence, t is 2; and M*, p, M, Z, X, L, X', x, l, and x' are as previously defined in claim 1.
3. A metal complex according to claim 1, corresponding to the formula:
structural isomers thereof wherein one or more double bonds occupy different positions within the various rings, or a mixture thereof, wherein:
T independently each occurrence is carbon, silicon, nitrogen, phosphorus, oxygen, sulfur, or boron;
J 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, hydrocarbyleneamino-substituted hydrocarbyl, di(hydrocarbyl)phosphino- substituted hydrocarbyl, hydrocarbylenephosphino-substituted hydrocarbyl, or hydrocarbylsulfido- substituted hydrocarbyl, said J group having up to 40 atoms not counting hydrogen atoms, and optionally two J groups together form a divalent derivative thereby forming a saturated or unsaturated ring, with the proviso that, in at least one occurrence, two or more of the foregoing J groups on different atoms, at least one or which is T, together form a divalent derivative, thereby forming at least one aromatic ring that is fused to the 6, 7, or 8 membered ring;
t is 0, 1 or 2; and, for compounds of formula (1A1) or (1A2) where T is carbon, in at least one occurrence, t is 2; and M, Z', X, L, X', x, 1, and x' are as previously defined in claim 1.
4. A compound or complex according to claim 1, corresponding to the formula:
structural isomers thereof wherein one or more double bonds occupy different positions within the various rings, and mixtures thereof, wherein J* 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, hydrocarbyleneamino-substituted hydrocarbyl, di(hydrocarbyl)phosphino- substituted hydrocarbyl, hydrocarbylenephosphino-substituted hydrocarbyl, or hydrocarbylsulfido- substituted hydrocarbyl, said J* group having up to 40 atoms not counting hydrogen atoms, and two J* groups together or a J* and a J' group together may form a divalent derivative thereby forming a saturated or unsaturated ring, with the proviso that, in at least one occurrence, two or more of the foregoing J* groups on different atoms, together form a divalent derivative, thereby forming at least one aromatic ring that is fused to the 6, 7, or 8 membered ring;
J' 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, hydrocarbyleneamino-substituted hydrocarbyl, di(hydrocarbyl)phosphino- substituted hydrocarbyl, hydrocarbylenephosphino-substituted hydrocarbyl, or hydrocarbylsulfido- substituted hydrocarbyl, said J' group having up to 40 atoms not counting hydrogen atoms, and two J' groups together or a J' group and a J*
group together may form a divalent derivative thereby forming a saturated or unsaturated fused ring;
M* is hydrogen, an alkali metal or an alkaline earth metal halide, T is carbon, boron, nitrogen or oxygen, t is 1 or 2;
t' is 0, 1 or 2, and M, X, L, X', x, 1, and x' are as defined in claim 3.
5. A metal compound or complex according to claim 4 corresponding to the formula:
wherein, T is carbon, or nitrogen;
when T is carbon, t' is 2, and when T is nitrogen, t'is 1;
M* is hydrogen, sodium, potassium, or lithium;
M is titanium;
R1 each occurrence is hydrogen or a hydrocarbyl, amino or amino- substituted hydrocarbyl group of up to 20 atoms other than hydrogen, and optionally two R' groups may be joined together;
Y is -O-, -S-, -NR5-, -PR5-; -NR5 2, or -PR5 2;
Z' is SiR6 2, CR6 2, SiR6 2SiR6 2, CR6 2CR6 2, CR6=CR6, CR6 2SiR6 2, BR6, BR6L", or GeR6 2;
R5 each occurrence is independently hydrocarbyl, trihydrocarbylsilyl, or trihydrocarbylsilylhydrocarbyl, said R5 having up to 20 atoms other than hydrogen, and optionally two R5 groups or R5 together with Y form a ring system ;
R6 each occurrence is independently hydrogen, or a member selected from hydrocarbyl, hydrocarbyloxy, silyl, halogenated alkyl, halogenated aryl, -NR5 2, and combinations thereof, said R6 having up to 20 non-hydrogen atoms, and optionally, two R6 groups form a ring system;
X, L, L",and X' are as previously defined;

x is 0, 1 or 2;
l is 0 or 1; and x'is 0 or 1;
with the proviso that:
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 -NR5 2 or -PR5 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 0,1 is 1, M is in the +2 formal oxidation state, and L
is a neutral, conjugated or nonconjugated diene, optionally substituted with one or more hydrocarbyl groups, said L having up to 40 carbon atoms and being bound to M by means of delocalized .pi.-electrons thereof.
6. A metal complex according to claim 1 that is:
(2,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethyl-silanamide titanium (II) 1,4-diphenyl-1,3-butadiene, (2,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethyl-silanamide titanium (II) 1,3-pentadiene, ((2,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethyl-silanamide titanium (III) 2-(N,N-dimethylamino)benzyl, (2,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethyl-silanamide titanium (IV) dichloride, 2,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethyl-silanamide titanium (IV) dimethyl, 2,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethyl-silanamide titanium (IV) dibenzyl, (2,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(cyclohexyl)dimethyl-silanamide titanium (II) 1,4-diphenyl-1,3-butadiene, (2,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(cyclohexyl)dimethyl-silanamide titanium (II) 1,3-pentadiene, ((2,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(cyclohexyl)dimethyl-silanamide titanium (III) 2-(N,N-dimethylamino)benzyl, (2,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(cyclohexyl)dimethyl-silanamide titanium (IV) dichloride, 2,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(cyclohexyl)dimethyl-silanamide titanium (IV) dimethyl, 2,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(cyclohexyl)dimethyl-silanamide titanium (IV) dibenzyl, (2,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethyl-silanamide titanium (II) 1,4-diphenyl-1,3-butadiene, (2,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethyl-silanamide titanium (II) 1,3-pentadiene, ((2,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethyl-silanamide titanium (III) 2-(N,N-dimethylamino)benzyl, (2,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethyl-silanamide titanium (IV) dichloride, 2,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethyl-silanamide titanium (IV) dimethyl, 2,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethyl-silanamide titanium (IV) dibenzyl, (2,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(cyclohexyl)dimethyl-silanamide titanium (II) 1,4-diphenyl-1,3-butadiene, (2,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(cyclohexyl)dimethyl-silanamide titanium (II) 1,3-pentadiene, ((2,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(cyclohexyl)dimethyl-silanamide titanium (III) 2-(N,N-dimethylamino)benzyl, (2,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(cyclohexyl)dimethyl-silanamide titanium (IV) dichloride, 2,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(cyclohexyl)dimethyl-silanamide titanium (IV) dimethyl, 2,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(cyclohexyl)dimethyl-silanamide titanium (IV) dibenzyl, or a mixture thereof.
7. 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 1-6.
8. The process of claim 7 wherein the catalyst composition additionally comprises an activating cocatalyst.
9. The process of claim 8 conducted under solution, slurry or high pressure polymerization conditions.
10. The process of claim 8 conducted under slurry or gas phase polymerization conditions, wherein the catalyst additionally comprises an inert, particulated support.
11. The process of claim 8 wherein the activating cocatalyst is (2,4,6-trifluorophenyl)dioctadecylammonium tetrakis(pentafluorophenyl)borate, (2,4,6-trifluorophenyl)dioctadecylammonium (hydroxyphenyl)tris(pentafluorophenyl)- borate, (2,4,6-trifluorophenyl)dioctadecylammonium (diethylaluminoxyphenyl)tris(pentafluoro-phenyl) borate, (pentafluorophenyl)dioctadecylammonium tetrakis(pentafluorophenyl)borate, (pentafluorophenyl)dioctadecylammonium (hydroxyphenyl)tris(pentafluorophenyl)-borate, (pentafluorophenyl)dioctadecylammonium (diethylaluminoxyphenyl)tris(pentafluoro-phenyl) borate, (p-trifluoromethylphenyl)dioctadecylammonium tetrakis(pentafluorophenyl)borate, (p-trifluoromethylphenyl)dioctadecylammonium (hydroxyphenyl)tris(pentafluoro-phenyl) borate, (p-trifluoromethylphenyl)dioctadecylammonium (diethylaluminoxyphenyl)tris(penta-fluorophenyl) borate, p-nitrophenyldioctadecylammonium tetrakis(pentafluorophenyl)borate, p-nitrophenyldioctadecylammonium (hydroxyphenyl)tris(pentafluorophenyl) borate, or p-nitrophenyldioctadecylammonium (diethylaluminoxyphenyl)tris(pentafluorophenyl) borate.
12. A process for preparing a polycyclic, fused ring cyclopentadiene compound comprising:
A) contacting 1) a cyclic compound containing ethylenic unsaturation in the ring forming atoms thereof and substituted at the .alpha.-position of such ethylenic unsaturation with a leaving group with 2) an acetylenic compound containing a protecting group at one of the acetylenic carbons and a group that is reactive with the leaving group of the cyclic compound at the remaining acetylenic carbon under conditions to cause ligand exchange, optionally in the presence of a base, thereby forming a cyclic compound containing ethylenic unsaturation and substituted at an .alpha.-carbon of the ethylenic unsaturation with an acetylenic group;

B) carbonylating and ring closing the product of step A) to form a polycyclic, fused ring cyclopentenone compound; and C) reducing and dehydrating the product of step B) to form the desired polycyclic, fused ring cyclopentadiene compound (III).
13. The process of claim 12 wherein the steps A), B) and C) are as follows:
A) B) C) where Le is a leaving group, Pr is a protecting group, T"-T" is the divalent remnant of the cyclic compound containing ethylenic unsaturation excluding the carbons forming the ethylenic unsaturation and Le, and M** is a group that is reactive with the leaving group, Le.
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