Olefin polymerization catalyst system Number:7,094,848 from the United States Patent and Trademark Office (PTO) owispatent

Title: Olefin polymerization catalyst system

Abstract: This invention relates to a compound represented by the formula: ##STR00001## wherein M is selected from groups 3 11 of the periodic table; ##STR00002## L.sup.1 represents a formal anionic ligand, L.sup.2 represents a formal neutral ligand, a is an integer greater than or equal to 1; b is greater than or equal to 0; c is greater than or equal to 1, E is nitrogen or phosphorus, Ar.sup.0 is arene, R.sup.1 R.sup.4 are, each independently, selected from hydrogen, hydrocarbyl, substituted hydrocarbyl or functional group, provided however that R.sup.3 and R.sup.4 do not form a naphthyl ring, N is nitrogen and O is oxygen.This invention further relates to a process to oligomerize and/or polymerize unsaturated monomers using the above compositions, optionally combined with an activator.

Patent Number: 7,094,848 Issued on 08/22/2006 to Hinkle,   et al.

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Inventors:	Hinkle; Paul Veinbergs (Houston, TX), Rix; Francis Charles (League City, TX)
Assignee:	ExxonMobil Chemical Patents Inc. (Houston, TX)
Appl. No.:	10/436,741
Filed:	May 13, 2003

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Current U.S. Class:	526/161 ; 502/155; 502/167; 526/171; 526/172; 526/348
Current International Class:	C08F 4/44 (20060101); B01J 31/38 (20060101)
Field of Search:	526/161,171,172,348 502/155,167

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References Cited [Referenced By]

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	96/23010		Aug., 1996		WO
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Other References

Younkin, T.R.; Connor, E.F.; Henderson, J.I.; Friederich, S.K.; Grubbs, R.H.; Bansleben, D.A.; "Neutral, Single-Component Nickel (II) Polyolefin Catalysts That Tolerate Heteroatoms", Science 2000, 287, 460-462. cited by other . Wang, C. Friederich, S.; Younkin, T.R.; Grubbs, R.H.; Bansleben, D.A.; Day, M.W.; "Neutral Nickel (II)-Based Catalysts for Ethylene Polymerization", Organometallics 1998, 17, 3149-3151. cited by other . Hicks, F.; Brookhart, M.; "A Highly Active Anilinotropone-Based Neutral Nickel (II) Catalyst for Ethylene Polymerization", Organometallics 2001, 20, 3217-3219. cited by other . Connor, E.F.; Younkin, T.R.; Henderson, J.I.; Hwang, S.; Grubbs, R.H.; Roberts, W.P.; Litzau, J.J., "Linear Functionalized Polyethylene Prepared with Highly Active Neutral Ni (II) Complexes", J. Pol. Sci. A. 2002, 40, 2842-2854. cited by other . Schroeder, D.L.; Keim, w.; Zuideveld, M.A.; Mecking, S, "Ethylene Polymerization by Novel, Easily Accesible Catalysts Based on Nickel (II) Diazene Complexes", Macromolecules, 2002, 35, 6071-6073. cited by other . Laali, K.; Szele, I.; Zollinger, H., "Dediazoniation of Arendediazonium Ion. Part XXII, Reactions of 2,6-Dialkyl-Substituted Benzenediazonium Ions in Super Acids, Acetonitrile and Acetone" Helvetica Chimica Acta 1983, 66, 1737-1747. cited by other . Petrillo, G.; Novi, M.; Garbarino, G.; Filiberti, M., The Reaction Between Arendiazonium Tetrafloroborates and Alkaline Thiocarboxylates in DMSO: A Convenient Access to Aryl Thiolesters and other Aromatic Sulfur Derivatives: Tetrahedron 1989, 45, 7411-7420. cited by other . Drent et al., "Palladium Catalysed Copolymerisation of Ethene with Alkylacrylates: Polar Comonomer Built into the Linear Polymer Chain", Chem. Commun. 2002, 744-745. cited by other . Stribrany et al., "Cu Catalysts for Homo- and Copolymerization of Olefins and Acrylates", Polymeric Materials: Science & Engineering 2002, 86, 325. cited by other . Stibrany et al., "Cu Catalysts for Homo- and Copolymerization of Olefins and Acrylates", Beyond Metallocenes: Next-Generation Polymerization Catalysts, ACS Symposium Series 857, Washington, DC. 2003, 222-230. cited by other . Wang et al., "Novel Nickel Catalysts for Ethylene/Polar Monomer Copolymerization", Polymeric Materials: Science & Engineering 2002, 86, 322. cited by other . Johnson et al., "Copolymerization of Ethylene and Propylene with Functionalized Vinyl Monomers by Palladium(II) Catalysts", J. Am. Chem. Soc. 1996, 118, 267-268. cited by other . Mecking et al., "Mechanistic Studies of the Palladium-Catalyzed Copolymerization of Ethylene and .alpha.-Olefins with Methyl Acrylate", J. Am. Chem. Soc. 1998, 120, 888-899. cited by other . Johnson et al., "Copolymerization of Ethylene and Acrylates by Nicket Catalysts", Polymeric Materials: Science & Engineering 2002, 86, 319. cit- ed by other . Liu et al., "Ethylene Polymerization and Ethylene/Methyl 10-Undecenoate Copolymerization Using Nickel(II) and Palladium(II) Complexes Derived from a Bulky P,O Chelating Ligand", Organometallics 2002, 21, 2836-2838. cited by other . Ittel et al., "Late-Metal Catalysts for Ethylene Homo- and Copolymerization", Chem. Rev. 2000, 100, 1169-1203. cited by other . Gibson et al., "Advances in Non-Metallocene Olefin Polymerization Catalysts", Chem. Rev. 2003, 103, 283-315. cited by other . Stibrany et al., "Polymerization and Copolymerization of Olefins and Acrylates by Bis(benzimidazole) Copper Catalysts", Macromolecules 2003, 36, 8584-8586. cited by other . Grubbs et al., "Neutral Single-Component Nickel (II) Polyolefin Catalysts That Tolerate Heteroatoms", Science, vol. 287, (Jan. 27, 2000), pp. 460-462. cited by other . Wang Et al., "Neutral Nickel(II)-Based Catalysts for Ethylene Polymerization", Organometallics, 1998, 17, pp. 3149-3151. cited by other.

Primary Examiner: Harlan; Robert D.
Attorney, Agent or Firm: Bell; Catherine L.

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Claims

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The invention claimed is:

1. A composition represented by the formula: ##STR00048## wherein ##STR00049## M is selected from groups 3 11 of the periodic table; E is nitrogen or phosphorus; Ar.sup.0 is arene; R.sup.1 R.sup.4 are, each independently, selected from hydrogen, hydrocarbyl, substituted hydrocarbyl or functional group, provided however that R.sup.3 and R.sup.4 do not form a naphthyl ring; L.sup.1 represents a formal anionic ligand, L.sup.2 represents a formal neutral ligand, a is an integer greater than or equal to 1; b is an integer greater than or equal to 0; and c is an integer greater than or equal to 1.

2. The composition of claim 1 wherein M is a group 4 or 10 metal.

3. The composition of claim 1 wherein M is titanium or nickel.

4. The composition of claim 1 wherein E is nitrogen.

5. The composition of claim 1 wherein a is 1, 2, 3, or 4.

6. The composition of claim 1 wherein a is 1 or 2.

7. The composition of claim 1 wherein b is 0, 1 or 2 and c is 1 or 2.

8. The composition of claim 1 wherein Ar.sup.0 is selected from the group consisting of ZETA-ARENES.

9. The composition of claim 1 further comprising an activator.

10. The composition of claim 1 wherein each L.sup.2 is, independently, selected from the group consisting of ethers, ketones, esters, alcohols, carboxylic acids, amines, imines, azo, nitriles, heterocycles, phosphines, thioethers, alkyls, alkenes, alkynes, arenes and combinations thereof; and each L.sup.1 is, independently, selected from the group consisting of hydrides, fluorides, chlorides, bromides, iodides, alkyls, aryls, alkenyls, alkynyls, allyls, benzyls, acyls, trimethylsilyls and combinations thereof; Ar.sup.0 is selected from the group consisting of substituted or unsubstituted heterocyclics, polyheterocyclics, heterocyclic ring assemblies, fused heterocyclic ring systems or combinations thereof.

11. The composition of claim 10 wherein M is nickel or titanium.

12. The composition of claim 11 wherein a=1 or 2, b=0, 1 or 2, and c=1 or 2.

13. The composition of claim 10 further comprising an activator.

14. The composition of claim 1 wherein L.sup.1 is selected from the group consisting of ZETA-FORMAL ANIONIC LIGANDS, and L.sup.2 is selected from the group consisting of ZETA-FORMAL NEUTRAL LIGANDS.

15. The composition of claim 1 wherein L.sup.1 is selected from the group consisting of --F, --Cl, --Br, --I, --N(CH.sub.3).sub.2, --OCH.sub.3, --H, --CH.sub.3, --C.sub.6H.sub.5, -allyl, -benzyl, --CH.sub.2Si(CH.sub.3).sub.3.

16. A composition represented by one of the following formulae: TABLE-US-00008 (L.sup.0).sub.a(L.sup.1).sub.b-2(L.sup.2).sub.cM(R.sup.5).sub.2 (L.sup.0)- .sub.a(L.sup.1).sub.b-2(L.sup.2).sub.cM(R.sup.5).sub.1(L.sup.3).sub.1 2 3 (L.sup.0).sub.a(L.sup.1).sub.b-2(L.sup.2).sub.cM(L.sup.3).sub.2 (L.sup.0)- .sub.a(L.sup.2).sub.cM 4 5 (L.sup.0).sub.a(L.sup.1).sub.b-1(L.sup.2).sub.cM(R.sup.5).sub.1 (L.sup.0)- .sub.a(L.sup.1).sub.b-1(L.sup.2).sub.cM(L.sup.3).sub.1 6 7

wherein: M is selected from groups 3 11 of the periodic table, L.sup.0 represents an E-phenoxide ligand represented by the formula: ##STR00050## L.sup.1 represents a formal anionic ligand; L.sup.2 represents a formal neutral ligand; L.sup.3 represents a formal anionic ligand that comprises a functional group; a is 1, 2, 3 or 4; b is 0, 1, 2, 3, 4, 5 or 6, provided that b is not 0 or 1 in formula 2, 3 or 4 and b is not 0 in formula 6 or 7; c is 1, 2, 3 or 4; E is nitrogen or phosphorus; Ar.sup.0 is an arene selected from the group consisting of ZETA-ARENES; R.sup.1 R.sup.4 are each independently hydrogen, a hydrocarbyl, a substituted hydrocarbyl or a functional group, provided that R.sup.3 and R.sup.4 do not form a naphthyl ring; and R.sup.5 is a hydride, a hydrocarbyl or a substituted hydrocarbyl.

17. The composition of claim 16 wherein E is nitrogen and M is titanium or nickel.

18. A composition represented by one of the following formulae: ##STR00051## E is nitrogen or phosphorus; Ar.sup.1 is selected from the group consisting of: ##STR00052## ##STR00053## R.sup.1 R.sup.4 are each independently hydrogen, a hydrocarbyl, a substituted a hydrocarbyl or a functional group, provided that R.sup.3 and R.sup.4 do not form a naphthyl ring; L.sup.1 represents a formal anionic ligand selected from the group consisting of ZETA-FORMAL ANIONIC LIGANDS; L.sup.2 represents a formal neutral ligand selected from the group consisting of ZETA-FORMAL NEUTRAL LIGANDS; "d" is 1, 2 or 3; A.sup.- is an anion that may or may not coordinate to Ni; and Z.sup.+ is a cation selected from the group consisting of metals or metal complexes of groups 1, 2, 11, and 12, Where Me is methyl, Et is ethyl, iPr is isopropyl, tBu is tertiary butyl, Ph is phenyl, p-t-BuPh is para-tertiary-butylphenyl.

19. The composition of claim 18 wherein A.sup.- is a non-coordinating anion.

20. The composition of claim 18 wherein A.sup.- is selected from the group consisting of halides, carboxylates, phosphates, sulfates, sulfonates, borates, aluminates, alkoxides, thioalkoxides, anonic substituted hydrocarbons, and anionic metal complexes.

21. A composition represented by formula: ##STR00054## wherein L.sup.1 represents a formal anionic ligand; R.sup.3 is hydrogen, a hydrocarbyl, a substituted hydrocarbyl or a functional group; R.sup.6 is C(R.sup.7).sub.e, e is 2 or 3, R.sup.7 is a hydrocarbon, a substituted hydrocarbon, or a functional group, two R.sup.7 groups may be part of a common arene ring when e is 2; Ar.sup.1 is an arene; and L.sup.4 is a formal neutral ligand, coordinated to the nickel in addition to the nitrogen of the azo-phenoxide ligand.

22. The composition of claim 21 wherein L.sup.4 selected from the group consisting of: ##STR00055## where Me is methyl.

23. The composition of claim 22 wherein R.sup.6 is selected from the group consisting of t-butyl, adamantyl, phenyl, naphthyl, and anthracenyl.

24. A composition represented by the formula: ##STR00056## wherein: L.sup.4 represents a formal neutral ligand based on carbon, nitrogen or phosphorus; R.sup.8 represents a formal anionic ligand which may be hydrogen or a hydrocarbyl; Ar.sup.2 is a phenyl group independently substituted in the 2 and 6 positions by secondary hydrocarbons, secondary substituted hydrocarbons, tertiary hydrocarbons, tertiary substituted hydrocarbons, or arenes Ar.sup.2 is an arene; Ar.sup.3 is an arene; and Me is methyl.

25. The composition of claim 24 wherein Ar.sup.2 is selected from the group ##STR00057## consisting of: where iPr is isopropyl, tBu is tertiary butyl and Ph is phenyl.

26. The composition of claim 24 wherein Ar.sup.3 is selected from the group consisting of: ##STR00058##

27. The composition of claim 24 wherein R.sup.8 is selected from the group consisting of hydrogen, a hydride, methyl, ethyl, trimethylsilylmethyl, trimethylsilyl, phenyl, naphthyl, allyl and benzyl.

28. A composition represented by the formula: ##STR00059## where R is tertiary butyl or anthracene and R' is methyl or tertiary butyl, iPr is isopropyl and Ph is phenyl.

29. A process to oligomerize unsaturated monomers comprising combining monomer, activator and the composition of claim 1.

30. A process to polymerize olefins comprising combining olefins, activator and the composition of claim 1.

31. A process to oligomerize unsaturated monomers comprising combining monomer and the composition of claim 1.

32. A process to polymerize olefins comprising combining olefins and the composition of claim 1.

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Description

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FIELD OF THE INVENTION

This invention relates to novel phenoxide-containing transition metal compounds and to processes to polymerize or oligomerize unsaturated monomers using phenoxide-containing transition metal compounds and polymers produced therefrom.

BACKGROUND OF THE INVENTION

The present invention is directed toward new transition metal compounds containing bidentate E-phenoxide ligands and formal neutral ligands that are useful for the oligomerization and polymerization of olefins. Bidentate E-phenoxide ligands form 6-membered metallacycle rings when bound to a transition metal. These compounds, and optionally an activator, can be used to oligomerize or polymerize unsaturated monomers such as olefins.

Other polymerization catalysts employing bidentate ligands based on phenoxide that form six-membered metallacycle rings have been reported in the art. Mitsui has reported low activity transition metal complexes containing azo-phenoxide ligands (European Patent EP-A1 0 990 664). Low activity, low molecular weight catalysts that use an azo-phenoxide ligand based upon a naphthyl ring have also been reported in the literature (Macromolecules, 2002, 35, 6071). Catalysts based upon keto-amide structures have been reported by Dupont (WO 98/30609). These show poor activity and low molecular weight or poor molecular weight control. Imine-phenoxide catalysts based on nickel have been reported both by Grubbs (Science 2000, 287, 460; Organometallics 1998, 17, 3149; J. Pol. Sci. A. 2002, 40, 2842; WO 98/42665; WO 2000/56786; WO 2000/56787; WO 2000/56781) and Dupont researchers (WO 98/30609). These imine-phenoxide systems were examined alongside the azo-phenoxide catalysts reported here and the imine-phenoxide systems were shown to give lower molecular weight polymer.

Other references of interest include:

1. Younkin, T. R.; Connor, E. F.; Henderson, J. I.; Friederich, S. K.; Grubbs, R. H.; Bansleben, D. A. Science 2000, 287, 460 2. Wang, C. Friederich, S.; Younkin, T. R.; Li, R. T.; Grubbs, R. H.; Bansleben, D. A.; Day, M. W. Organometallics 1998, 17, 3149. 3. Johnson, L. K.; Bennett, A. M. A.; Wang, L.; Parthasarathy, A.; Hauptman, E.; Simpson, R. D.; Feldman, J.; Coughlin, E. B. WO 98/30609 4. Bansleben, D. A.; Friederich, S. K.; Younkin, T. R.; Grubbs, R. H.; Wang, C.; Li, R. T. WO 98/42664 5. Bansleben, D. A.; Friederich, S. K.; Younkin, T. R.; Grubbs, R. H.; Wang, C.; Li, R. T. WO 98/42665 6. Bansleben, D. A.; Connor, E. F.; Grubbs, R. H.; Henderson, J. I.; Younkin, T. R.; Nadjadi, A. R. WO 2000/56786 7. Bansleben, D. A.; Connor, E. F.; Grubbs, R. H.; Henderson, J. I.; Younkin, T. R.; Nadjadi, A. R. WO 2000/56787 8. Bansleben, D. A.; Friedrich, S. K.; Grubbs, R. H.; Li, R. T.; Connor, E. F.; Roberts, W.P. Wo 2000/56781 9. Hicks, F.; Brookhart, M. Organometallics 2001, 20, 3217 10. Connor, E. F.; Younkin, T. R.; Henderson, J. I.; Hwang, S.; Grubbs, R. H.; Roberts, W. P.; Litzau, J. J. J. Pol. Sci. A.. 2002, 40, 2842 11. Schroeder, D. L.; Keim, w.; Zuideveld, M. A.; Mecking, S, Macromolecules, 2002, 35, 6071 12. Matsui, S.; Nitabaru, M.; Tsuru, K.; Fujita, T.; Suzuki, Y.; Takagi, Y.; Tanaka, H. EP 0 990 664 A1 13. Laali, K.; Szele, I.; Zollinger, H., Helvetica Chimica Acta 1983, 66, 1737 14. Petrillo, G.; Novi, M.; Garbarino, G.; Filiberti, M., Tetrahedron 1989, 45, 7411

SUMMARY OF THE INVENTION

This invention relates to a compound represented by the formula:

##STR00003## wherein M is selected from groups 3 11 of the periodic table;

##STR00004## L.sup.1 represents a formal anionic ligand, L.sup.2 represents a formal neutral ligand, a is an integer greater than or equal to 1; b is an integer greater than or equal to 0; c is an integer greater than or equal to 1, E is nitrogen or phosphorus, Ar.sup.0 is arene, R.sup.1 R.sup.4 are, each independently, selected from hydrogen, hydrocarbyl, substituted hydrocarbyl or functional group, provided however that R.sup.3 and R.sup.4 do not form a naphthyl ring, N is nitrogen, and O is oxygen.

This invention further relates to a process to oligomerize and/or polymerize unsaturated monomers using the above compositions, optionally combined with an activator.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a plot of Mw (k, calculated using polystyrene standard) versus ethylene pressure.

FIG. 2 is a plot of Mw (k, calculated using polystyrene standard) versus equivalent of B(C.sub.6F.sub.5).sub.3 at 264 psig. The plot indicates that at 264 psig the Mw capabilities of the azo precatalysts are comparable or better than the corresponding imine catalysts.

FIG. 3 is a comparison of Mw (k) vs. mol % octene incorporated from the data in Table 3.

DETAILED DESCRIPTION OF THE INVENTION

This invention relates to a new class of catalyst compounds that may be combined with one or more activators to oligomerize or polymerize any unsaturated monomer.

For the purposes of this invention and the claims thereto when a polymer is referred to as comprising a monomer, the momomer present in the polymer is the polymerized form of the monomer. For the purposes of this invention and the claims thereto when a polymer is referred to as comprising an olefin, the olefin present in the polymer is the polymerized form of the olefin. In the description herein the transition metal catalyst compound may be described as a catalyst precursor, a pre-catalyst compound, a transition metal complex or a catalyst compound, and these terms are used interchangeably. A catalyst system is a combination of a transition metal catalyst compound and an activator. An activator is also interchangeably referred to as a cocatalyst. In addition, a reactor is any container(s) in which a chemical reaction occurs.

As used herein, the numbering scheme for the Periodic Table Groups is used as in CHEMICAL AND ENGINEERING NEWS, 63(5), 27 (1985).

Further for purposes of this invention Me is methyl, Ph is phenyl, Et is ethyl, Pr is propyl, iPr is isopropyl, n-Pr is normal propyl, Bu is butyl, iBu is isobutyl, tBu is tertiary butyl, p-tBu is para-tertiary butyl, and TMS is trimethylsilyl.

This invention further relates to processes for preparing oligomers and/or polymers of unsaturated monomers, such as polar monomers and or olefins comprising contacting a transition metal compound (as described herein) and, optionally, an activator with the monomers.

The metal compound preferably contains at least one E-phenoxide ligand (L.sup.0), and at least one formal neutral ligand (L.sup.2). The remaining ligands in the coordination sphere of the metal compound typically are such that the compound attains a d electron count of 14 18. The d electron count is the formal sum of the metal's d electrons plus those contributed by the ligands.

Preferred E-phenoxide metal compounds are represented by formula:

##STR00005## wherein: M is selected from groups 3 11 of the periodic table, preferably group 4 or 10, more preferably Ti or Ni; L.sup.0 represents an E-phenoxide ligand represented by the formula:

##STR00006## wherein: E is nitrogen or phosphorus, preferably nitrogen; Ar.sup.0 is arene; R.sup.1 R.sup.4 are each independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl or functional group, provided that R.sup.3 and R.sup.4 do not form a naphthyl ring; L.sup.1 represents a formal anionic ligand; L.sup.2 represents a formal neutral ligand; a is an integer greater than or equal to 1, preferably a=1, 2, 3 or 4, preferably a=1 or 2; b is an integer greater than or equal to 0, preferably b is 0, 1, 2, 3, 4, 5 or 6, more preferably b=0, 1 or 2; and c is an integer greater than or equal to 1, preferably c=1, 2, 3 or 4, more preferably 1 or 2.

The metal compound may be neutral or a charged species with a counterion.

The metal compound preferably contains at least one formal neutral ligand coordinated to the metal in addition to the nitrogen or phosphorus of the E-phenoxide ligand(s). Formal neutral ligands are defined as ligands that are neutral, with respect to charge, when formally removed from the metal in their closed shell electronic state. Formal neutral ligands contain at least one lone pair of electrons, pi-bond or sigma bond that are capable of binding to the transition metal. Formal neutral ligands may also be polydentate when more than one formal neutral ligand is connected via a bond or a hydrocarbyl, substituted hydrocarbyl or a functional group tether. A formal neutral ligand may be a substituent of another metal compound, either the same or different, such that multiple compounds are bound together.

Formal neutral ligands may be composed of combinations of hydrocarbyl, substituted hydrocarbyl, and functional groups. Non-limiting examples of formal neutral ligands are ethers, ketones, esters, alcohols, carboxylic acids, amines, imines, azo, nitriles, heterocycles, phosphines, thioethers, alkyls, alkenes, alkynes, and arenes.

For purposes of this invention and the claims thereto "ZETA FORMAL NEUTRAL LIGANDS" are defined to be formal neutral ligands represented by the following formulae: P(C(CH.sub.3).sub.3).sub.3 P(C.sub.6H.sub.11).sub.3 P(CH(CH.sub.3).sub.2).sub.3 P(CH.sub.2CH.sub.2CH.sub.3).sub.3 P(CH.sub.2CH.sub.3).sub.3 P(CH.sub.3).sub.3 P(C.sub.6H.sub.4OCH.sub.3).sub.3 P(CH.sub.2C.sub.6H.sub.5).sub.3 P(C.sub.6H.sub.4CH.sub.3) P(C.sub.6H.sub.5).sub.3 P(CH.dbd.CH.sub.2).sub.3 P(C.sub.6H.sub.4F).sub.3 P(C.sub.6H.sub.4Cl).sub.3 P(C.sub.2H.sub.5).sub.2C.sub.6H.sub.5P(CH.sub.3).sub.2C.sub.6H.sub.5 P(C.sub.6H.sub.5).sub.2CH.sub.3 P(C.sub.6H.sub.5).sub.2NMe.sub.2 P(C.sub.6H.sub.5)CH.sub.2C.sub.6H.sub.5 P(C.sub.6H.sub.5).sub.2(C.sub.6H.sub.4OCH.sub.3) P(C.sub.6H.sub.5)(CH.sub.2C.sub.6H.sub.5).sub.2 P(C.sub.6H.sub.5).sub.2(CH.dbd.CH.sub.2) P(C.sub.6H.sub.5).sub.2(C.sub.6H.sub.4F) P(OCH.sub.2CH.sub.3)(C.sub.6H.sub.5).sub.2 P(OCH(CH.sub.3).sub.2).sub.2C.sub.6H.sub.5 PH(C.sub.6H.sub.5).sub.2 P(OCH.sub.2CH.sub.2CH.sub.3).sub.2C.sub.6H.sub.5 P(OC.sub.6H.sub.5)(C.sub.6H.sub.5).sub.2 P(C.sub.6H.sub.5).sub.2C.sub.6F.sub.5 PPh.sub.2(C.sub.6H.sub.4Cl) P(C.sub.6H.sub.3(OCH.sub.3).sub.2).sub.3 P(C.sub.6H.sub.5).sub.2(C.sub.6H.sub.4N(CH.sub.3).sub.2) P(C.sub.6H.sub.2(CH.sub.3).sub.3).sub.3 P(C.sub.6H.sub.5).sub.2(C.sub.6H.sub.2(CH.sub.3).sub.3) P(C.sub.6H.sub.5)(C.sub.6F.sub.5).sub.2 P(C.sub.6F.sub.5).sub.3 P(C.sub.10H.sub.7).sub.3 Me.sub.3P.dbd.CH.sub.2 (C.sub.6H.sub.5).sub.3P.dbd.CH.sub.2 H.sub.2C.dbd.CH.sub.2 H.sub.2C.dbd.CHCH.sub.3 H.sub.2C.dbd.CH.sub.2CH.sub.2CH.sub.3 CH.sub.3CH.dbd.CHCH.sub.3 H.sub.2C.dbd.CH.sub.2CH.sub.2CH.sub.2CH.sub.3 CH.sub.3CH.dbd.CHCH.sub.2CH.sub.3 H.sub.2C.dbd.CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.3 CH.sub.3CH.dbd.CHCH.sub.2CH.sub.2CH.sub.3 CH.sub.3CH.sub.2CH.dbd.CHCH.sub.2CH.sub.3 CH.sub.3CH.dbd.CHCH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.3 CH.sub.3CH.sub.2CH.dbd.CHCH.sub.2CH.sub.2CH.sub.2CH.sub.3 H.sub.2C.dbd.CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.3 CH.sub.3CH.sub.2CH.sub.2CH.dbd.CHCH.sub.2CH.sub.2CH.sub.3 CH.sub.3CH(CH.sub.3)CH.dbd.CH.sub.2 C(CH.sub.3).sub.3CH.dbd.CH.sub.2 (CH.sub.3).sub.2C.dbd.CH.sub.2 CH.sub.3CH.sub.2CH(CH.sub.3)CH.dbd.CH.sub.2 H.sub.2C.dbd.CH.CH.dbd.CH.sub.2 CH.sub.3CH.dbd.CH.CH.dbd.CH.sub.2 CH.sub.3CH.dbd.CH.CH.dbd.CHCH.sub.3 H.sub.2C.dbd.C(CH.sub.3)--(CH.sub.3)C.dbd.CH.sub.2 (CH.sub.3CH.sub.2).sub.2C.dbd.CH.sub.2 H.sub.2C.dbd.C(CH.sub.3)--CH.dbd.CH.sub.2 H.sub.2C.dbd.CH--CH.sub.2).sub.1--CH.dbd.CH.sub.2 H.sub.2C.dbd.CH--CH.sub.2).sub.2--CH.dbd.CH.sub.2 H.sub.2C.dbd.CH--CH.sub.2).sub.3--CH.dbd.CH.sub.2 H.sub.2C.dbd.CH--CH.sub.2).sub.4--CH.dbd.CH.sub.2 H.sub.2C.dbd.CH--CH.sub.2).sub.1--CH.dbd.C(CH.sub.3).sub.2 H.sub.2C.dbd.CH--CH.sub.2).sub.2--CH.dbd.C(CH.sub.3).sub.2 H.sub.2C.dbd.CH--CH.sub.2).sub.3--CH.dbd.C(CH.sub.3).sub.2 H.sub.2C.dbd.CH--CH.sub.2).sub.4--CH.dbd.C(CH.sub.3).sub.2 (C.sub.6H.sub.5)CH.dbd.CH--CH.dbd.CH.sub.2 (C.sub.6H.sub.5)CH.dbd.CH--CH.dbd.CH(C.sub.6H.sub.5) CH.sub.2.dbd.CH--CH.sub.2CH.dbd.CHCH.sub.3 CH.sub.2.dbd.CH--CH.sub.2C(CH.sub.3).dbd.CHCH.sub.3 CH.sub.2.dbd.C(CH.sub.3)--CH.sub.2CH.dbd.CHCH.sub.3 CH.sub.2.dbd.C(CH.sub.3)--CH.sub.2CH.sub.3

##STR00007##

Formal anionic ligands are defined as ligands that are anionic, with respect to charge, when formally removed from the metal in their closed shell electronic state. Formal anionic ligands include hydride, halide, hydrocarbyl, substituted hydrocarbyl or functional group. Non-limiting examples of formal anionic ligands include hydride, fluoride, chloride, bromide, iodide, alkyl, aryl, alkenyl, alkynyl, allyl, benzyl, acyl, trimethylsilyl. Formal anionic ligands may also be polydentate when more than one formal anionic ligand is connected via a bond or a hydrocarbyl, substituted hydrocarbyl or a functional group tether. A formal anionic ligand may be a substituent of another metal compound, either the same or different, such that multiple compounds are bound together.

For purposes of this invention and the claims thereto "ZETA-FORMAL ANIONIC LIGANDS" is defined to be the group of formal anionic ligands represented by the following formulae: --F--Cl--Br--I--CN--NO.sub.2 --N(CH.sub.3).sub.2 --N(CH.sub.2CH.sub.3).sub.2 --N(Si(CH.sub.3).sub.3).sub.2 --N(CH.sub.3)(Si(CH.sub.3).sub.3) --OC(O)CH.sub.3 --OC(O)CF.sub.3 --S(O).sub.2CH.sub.3 --OS(O).sub.2CH.sub.3 --OS(O).sub.2C.sub.6H.sub.4CH.sub.3 --OS(O).sub.2CF.sub.3 --OS(O).sub.2C.sub.6H.sub.4NO.sub.2 --OS(O).sub.2C.sub.4F.sub.9 --OS(O).sub.2C.sub.6H.sub.4Br --SC.sub.6H.sub.5 --N.dbd.N--C.sub.6H.sub.5 --OCH.sub.3 --OCH.sub.2CH.sub.3 --OC(CH.sub.3).sub.2H --O(CH.sub.3).sub.3 --CF.sub.3 --C(O)H --C(O)CH.sub.3 --H --CH.sub.3 --CH.sub.2CH.sub.3 --CH(CH.sub.3).sub.2 --C(CH.sub.3).sub.3 --CH.dbd.CH.sub.2 --C.ident.CH --CH.sub.2C.sub.6H.sub.5 --CH.sub.2Si(CH.sub.3).sub.3 --C.sub.6H.sub.5 --C.sub.10H.sub.7 --CH.sub.2C(CH.sub.3).sub.3 --CH.sub.2CH.sub.2C(CH.sub.3).sub.3

##STR00008##

More preferred formal anionic ligands include: --F, --Cl, --Br, --I, --N(CH.sub.3).sub.2, --OCH.sub.3, --H, --CH.sub.3, --C.sub.6H.sub.5, -Allyl, -Benzyl, --CH.sub.2Si(CH.sub.3).sub.3.

Preferred non-limiting examples of formal anionic ligand that comprises a functional group include: --F--Cl--Br--I--CN--NO.sub.2 --N(CH.sub.3).sub.2 --N(CH.sub.2CH.sub.3).sub.2 --N(Si(CH.sub.3).sub.3).sub.2 --N(CH.sub.3)(Si(CH.sub.3).sub.3) --OC(O)CH.sub.3 --OC(O)CF.sub.3 --S(O).sub.2CH.sub.3 --OS(O).sub.2CH.sub.3 --OS(O).sub.2C.sub.6H.sub.4CH.sub.3 --OS(O).sub.2CF.sub.3 --OS(O).sub.2C.sub.6H.sub.4NO.sub.2 --OS(O).sub.2C.sub.4F.sub.9 --OS(O).sub.2C.sub.6H.sub.4Br --SC.sub.6H.sub.5 --N.dbd.N--C.sub.6H.sub.5 --OCH.sub.3 --OCH.sub.2CH.sub.3 --OC(CH.sub.3).sub.2H --O(CH.sub.3).sub.3

More preferred formal anionic ligands that comprise functional groups include: --F, --Cl, --Br, --I, --N(CH.sub.3).sub.2, --OCH.sub.3.

Using this nomenclature of anionic and neutral ligands, the ligands may be categorized as combinations of anionic and neutral ligands as when L.sup.1 and L.sup.2 are connected via a bond or a hydrocarbyl, substituted hydrocarbyl or a functional group tether. Preferred non-limiting examples of L.sup.1, L.sup.2 that meet this definition include ethyl, norbornyl, allyl, benzyl, CH.sub.2CH.sub.2C(O)Me, 1-(2-N(CH.sub.3).sub.2C.sub.6H.sub.4), acetylacetonate. The capability of hydrocarbyl groups, such as ethyl and norbomyl, to coordinate as a formal ligand (M-C sigma bond) and a formal neutral ligand, via an agostic 3 center-2 interaction between C, H and M is well recognized.

Monodentate ligands that are capable of multiple bonding to the metal may be categorized as combinations of anionic and neutral ligands. Ligands which display this behavior are functional groups that in addition to being a formal anionic ligand, have at least one pair of electrons, either localized or in a bonding arrangement with another atom or atoms, that also interact with the metal.

Non-limiting examples of such ligands are oxo, imido, carbene and Preferred non-limiting examples include: .dbd.O.dbd.CPh.sub.2 .dbd.CH.sub.2 .dbd.CHPh .dbd.CH(C.sub.6H.sub.2(CH.sub.3).sub.3) .ident.C--C.sub.6H.sub.2(CH.sub.3).sub.3 .ident.C--C.sub.6H.sub.3(CH(CH.sub.3).sub.2 .ident.N--C.sub.6H.sub.2(CH.sub.3).sub.3 .ident.N--C.sub.6H.sub.3(CH(CH.sub.3).sub.2

Preferred non-limiting examples of hydrocarbyl groups include: --H--CH.sub.3 --CH.sub.2CH.sub.3 --CH(CH.sub.3).sub.2 --C(CH.sub.3).sub.3 --CH.dbd.CH.sub.2 --C.ident.CH --CH.sub.2C.sub.6H.sub.5 --CH.sub.2Si(CH.sub.3).sub.3 --C.sub.6H.sub.5 --C.sub.10H.sub.7 --CH.sub.2C(CH.sub.3).sub.3 --CH.sub.2CH.sub.2C(CH.sub.3).sub.3

##STR00009## --SiMe.sub.3

Substituted hydrocarbyl radicals (also called substituted hydrocarbyls) are radicals in which at least one hydrocarbyl hydrogen atom has been substituted with at least one heteroatom or heteroatom containing group.

Preferred non-limiting examples of substituted hydrocarbyls include:

##STR00010##

The term "hydrocarbyl radical" is sometimes used interchangeably with "hydrocarbyl" throughout this document. For purposes of this disclosure, "hydrocarbyl radical" encompasses radicals containing carbon hydrogen and optionally silicon atoms, preferably 1 to 100 carbon atoms, hydrogen and optionally silicon. These radicals can be linear, branched, or cyclic including polycyclic. These radicals can be saturated, partially unsaturated or fully unsaturated, and when cyclic, may be aromatic or non-aromatic.

In some embodiments, the hydrocarbyl radical is selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, heneicosenyl, docosenyl, tricosenyl, tetracosenyl, pentacosenyl, hexacosenyl, heptacosenyl, octacosenyl, nonacosenyl, triacontenyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl, heptadecynyl, octadecynyl, nonadecynyl, eicosynyl, heneicosynyl, docosynyl, tricosynyl, tetracosynyl, pentacosynyl, hexacosynyl, heptacosynyl, octacosynyl, nonacosynyl, or triacontynyl isomers. For this disclosure, when a radical is listed it indicates that radical type and all other radicals formed when that radical type is subjected to the substitutions defined above. Alkyl, alkenyl and alkynyl radicals listed include all isomers including where appropriate cyclic isomers, for example, butyl includes n-butyl, 2-methylpropyl, 1-methylpropyl, tert-butyl, and cyclobutyl (and analogous substituted cyclopropyls); pentyl includes n-pentyl, cyclopentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl, and neopentyl (and analogous substituted cyclobutyls and cyclopropyls); butenyl includes E and Z forms of 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl and 2-methyl-2-propenyl (and cyclobutenyls and cyclopropenyls). Cyclic compound having substitutions include all isomer forms, for example, methylphenyl would include ortho-methylphenyl, meta-methylphenyl and para-methylphenyl; dimethylphenyl would include 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-diphenylmethyl, 3,4-dimethylphenyl, and 3,5-dimethylphenyl.

An arene is a substituted or unsubstituted aromatic hydrocarbon. Arenes may be monocyclic, polycyclic, hydrocarbon ring assemblies or fused ring systems. Arenes may be substituted or unsubstituted heterocyclics, polyheterocyclics, heterocyclic ring assemblies or fused heterocyclic ring systems. (In the formulae below, Z.sup.+ is a cation, preferably a metal or metal compound of groups 1, 2, 11, or 12 and A.sup.- is an anion.) For purposes of this invention and the claims thereto the term "ZETA-ARENES" is defined to be the group of arenes represented by the following formulae:

##STR00011## ##STR00012## ##STR00013## ##STR00014## ##STR00015## ##STR00016## ##STR00017## ##STR00018## ##STR00019## ##STR00020## ##STR00021## ##STR00022## ##STR00023## ##STR00024## ##STR00025## ##STR00026## ##STR00027## ##STR00028## ##STR00029## ##STR00030## ##STR00031## ##STR00032## ##STR00033## ##STR00034##

Functional groups are heteroatoms of groups 1 17 of the periodic table either alone or connected to other elements by covalent or other interactions such as ionic, van der Waals forces, or hydrogen bonding. Examples of functional groups include carboxylic acid, acid halide, carboxylic ester, carboxylic salt, carboxylic anhydride, aldehyde and their chalcogen (Group 14) analogues, alcohol and phenol, ether, peroxide and hydroperoxide, carboxylic amide, hydrazide and imide, amidine and other nitrogen analogues of amides, nitrile, amine and imine, azo, nitro, other nitrogen compounds, sulfur acids, selenium acids, thiols, sulfides, sulfoxides, sulfones, phosphines, phosphates, other phosphorus compounds, silanes, boranes, borates, alanes, aluminates. Functional groups may also be taken broadly to include organic polymer supports or inorganic support material such as alumina, and silica.

The nomenclature of d electron count, anionic ligands, neutral ligands, and oxidation state used here are described in length in the texts: Hegedus, L. S. Transition Metals in the Synthesis of Complex Organic Molecules 2nd Ed, University Science Press, 1999, Sausalito, Calif. and Collman, J. P. et. al. Principles and Applications of Organotransition Metal Chemistry. University Science Press, 1987, Sausalito, Calif.

Preferred E-phenoxide metal compounds include those represented by the following formulae:

TABLE-US-00001 (L.sup.0).sub.a(L.sup.1).sub.b-2(L.sup.2).sub.cM(R.sup.5).sub.2 (L.sup.0)- .sub.a(L.sup.1).sub.b-2(L.sup.2).sub.cM(R.sup.5).sub.1(L.sup.3).sub.1 2 3 (L.sup.0).sub.a(L.sup.1).sub.b-2(L.sup.2).sub.cM(L.sup.3).sub.2 (L.sup.0)- .sub.a(L.sup.2).sub.cM 4 5 (L.sup.0).sub.a(L.sup.1).sub.b-1(L.sup.2).sub.cM(R.sup.5).sub.1 (L.sup.0)- .sub.a(L.sup.1).sub.b-1(L.sup.2).sub.cM(L.sup.3).sub.1 6 7

wherein: M is selected from groups 3 11 of the periodic table, preferably group 4 or 10, more preferably Ti or Ni. L.sup.0 represents an E-phenoxide ligand represented by the formula:

##STR00035## L.sup.1 represents a formal anionic ligand; L.sup.2 represents a formal neutral ligand; L.sup.3 represents a formal anionic ligand that comprises a functional group; a is greater than or equal to 1, preferably a=1, 2, 3 or 4, preferably a=1 or 2; b is greater than or equal to 0, preferably b is 0, 1, 2, 3, 4, 5 or 6, more preferably b=0, 1 or 2, provided that b is not 0 or 1 in formula 2, 3 or 4 and b is not 0 in formula 6 or 7; c is greater than or equal to 1, preferably c=1, 2, 3 or 4, more preferably 1 or 2; E is nitrogen or phosphorus, preferably nitrogen; N is nitrogen; O is oxygen; Ar.sup.0 is an arene; R.sup.1 R.sup.4 are each independently hydrogen, a hydrocarbyl, a substituted hydrocarbyl or a functional group, provided that R.sup.3 and R.sup.4 do not form a naphthyl ring; and R.sup.5 is a hydride, a hydrocarbyl or a substituted hydrocarbyl.

Additional preferred E-phenoxide metal compounds include those represented by the following formulae:

##STR00036## E is nitrogen or phosphorus, preferably nitrogen; N is nitrogen; O is oxygen Ar.sup.1 is arene; preferably one or more of:

##STR00037## ##STR00038## R.sup.1 R.sup.4 are each independently hydrogen, a hydrocarbyl, a substituted a hydrocarbyl or a functional group, provided that R.sup.3 and R.sup.4 do not form a naphthyl ring; L.sup.1 represents a formal anionic ligand; L.sup.2 represents a formal neutral ligand; "d" equals 1, 2 or 3, preferably 2; A.sup.- is an anion that may or may not coordinate to Ni or may coordinate weakly to N; A.sup.- may be a non-coordinating anion, a substituted hydrocarbon or a functional group, preferably A.sup.- comprises one or more halides, carboxylates, phosphates, sulfates, sulfonates, borates, aluminates, alkoxides, thioalkoxides, anonic substituted hydrocarbons, or anionic metal complexes; Z.sup.+ is a cation, preferably a metal or metal complex of groups 1, 2, 11, or 12.

Preferably, the metal compound contains at least one formal neutral ligand coordinated to the metal in addition to the nitrogen or phosphorus of the E-phenoxide ligand(s).

The nickel compounds contain one E-phenoxide ligand and at least one formal neutral ligand. The remaining ligands in the coordination sphere of the metal compound are such that the compound attains a d electron count of 14 18. The nickel compound may be neutral or a charged species with an appropriate counterion.

Preferred metal compounds include those containing one azo-phenoxide ligand, one formal neutral ligand, and one formal anionic ligand.

Additional preferred azo-phenoxide metal compounds are represented by formula 11 and its steroisomers:

##STR00039## L.sup.1 represents a formal anionic ligand; R.sup.3 is hydrogen, a hydrocarbyl, a substituted hydrocarbyl or a functional group; R.sup.6 is C(R.sup.7).sub.e, e=2 or 3, R.sup.7 is a hydrocarbon, a substituted hydrocarbon, or a functional group, two R.sup.7 groups may be part of a common arene ring when e=2; Preferred non-limiting examples of R.sup.6 include t-butyl, adamantyl, phenyl, naphthyl, anthracenyl. Ar.sup.1 is an arene; L.sup.4, is a formal neutral ligand, coordinated to the nickel in addition to the nitrogen of the azo-phenoxide ligand, based on carbon, nitrogen or phosphorus, preferably one or more alkenes, alkynes, nitriles, pyridines, aryl phosphines and phosphorus ylides. Non-limiting preferred examples of L.sup.4 include:

##STR00040##

Particularly preferred azo-phenoxide compounds are represented by formula 12:

##STR00041## wherein: L.sup.4 represents a formal neutral ligand based on carbon, nitrogen or phosphorus preferably one or more alkenes, alkynes, nitriles, pyridines, aryl phosphines and or phosphorus ylides; R.sup.8 represents a formal anionic ligand which may be hydrogen or a hydrocarbon, preferably a hydride, methyl, ethyl, trimethylsilylmethyl, trimethylsilyl, phenyl, naphthyl, allyl, benzyl; Ar.sup.2 is a phenyl group substituted in the 2 and 6 positions by 2.degree. hydrocarbons, 2.degree. substituted hydrocarbons, 3.degree. hydrocarbons, 3.degree. substituted hydrocarbons, or arenes; Me is methyl. Preferred non-limiting examples of Ar.sup.2 include:

##STR00042##

For purposes of this invention, where the terms 2.degree. and 3.degree. are used we mean that the hydrocarbon is 2.degree. or 3.degree. prior to substitution onto the arene ring. For example in the structures above the iPr is 2.degree. and the tBu is 3.degree.. Ar.sup.3 is an arene. Preferred non-limiting examples of Ar.sup.3 include:

##STR00043##

In another preferred embodiment the catalyst compounds described herein may be used in combination with other polymerization and or oligomerization catalysts. In a preferred embodiment the instant catalyst compounds are used in combination with catalyst compounds described in any of the following references: 1. Younkin, T. R.; Connor, E. F.; Henderson, J. I.; Friederich, S. K.; Grubbs, R. H.; Bansleben, D. A. Science 2000, 287, 460 2. Wang, C. Friederich, S.; Younkin, T. R.; Li, R. T.; Grubbs, R. H.; Bansleben, D. A.; Day, M. W. Organometallics 1998, 17, 3149. 3. Johnson, L. K.; Bennett, A. M. A.; Wang, L.; Parthasarathy, A.; Hauptman, E.; Simpson, R. D.; Feldman, J.; Coughlin, E. B. WO 98/30609 4. Bansleben, D. A.; Friederich, S. K.; Younkin, T. R.; Grubbs, R. H.; Wang, C.; Li, R. T. WO 98/42664 5. Bansleben, D. A.; Friederich, S. K.; Younkin, T. R.; Grubbs, R. H.; Wang, C.; Li, R. T. WO 98/42665 6. Bansleben, D. A.; Connor, E. F.; Grubbs, R. H.; Henderson, J. I.; Younkin, T. R.; Nadjadi, A. R. WO 2000/56786 7. Bansleben, D. A.; Connor, E. F.; Grubbs, R. H.; Henderson, J. I.; Younkin, T. R.; Nadjadi, A. R. WO 2000/56787 8. Bansleben, D. A.; Friedrich, S. K.; Grubbs, R. H.; Li, R. T.; Connor, E. F.; Roberts, W. P. Wo 2000/56781 9. Hicks, F.; Brookhart, M. Organometallics 2001, 20, 3217 10. Connor, E. F.; Younkin, T. R.; Henderson, J. I.; Hwang, S.; Grubbs, R. H.; Roberts, W. P.; Litzau, J. J. J. Pol. Sci. A. 2002, 40, 2842 11. Schroeder, D. L.; Keim, w.; Zuideveld, M. A.; Mecking, S, Macromolecules, 2002, 35, 6071 12. Matsui, S.; Nitabaru, M.; Tsuru, K.; Fujita, T.; Suzuki, Y.; Takagi, Y.; Tanaka, H. EP 0 990 664 A1 13. Laali, K.; Szele, I.; Zollinger, H., Helvetica Chimica Acta 1983, 66, 1737 14. Petrillo, G.; Novi, M.; Garbarino, G.; Filiberti, M., Tetrahedron 1989, 45, 7411 15. WO 98/30609 16. Grubbs (Science 2000, 287, 460; Organometallics 1998, 17, 3149; J Pol. Sci. A. 2002, 40, 2842) 17. WO 98/42665 18. WO 2000/56786 19. WO 2000/56787 20. WO 2000/56781 21. WO 98/30609. Activators and Activation Methods for Catalyst Compounds

An activator is defined as any combination of reagents that increases the rate at which a metal compound, containing at least one E-Phenoxide ligand and one formal neutral ligand, oligomerizes or polymerizes unsaturated monomers, such as olefins. An activator may also affect the molecular weight, degree of branching, comonomer content, or other properties of the oligomer or polymer. The E-phenoxide compounds according to the invention may be activated for oligomerization and or polymerization catalysis in any manner sufficient to allow coordination or cationic oligomerization and or coordination or cationic polymerization.

Generally speaking, successful olefin oligomerization and/or polymerization catalysts contain a formal anionic ligand, such as hydride or hydrocarbyl, with an adjacent (cis) coordination site accessible to an unsaturated monomer. Coordination of an unsaturated monomer to the cis coordination site allows a migratory insertion reaction to form a metal alkyl. Repetition of this process causes chain growth. An activator is thus any combination of reagents that facilitates formation of a transition metal compound containing, in addition to at least one E-phenoxide ligand, cis coordinated olefin and hydride or hydrocarbyl.

When the E-phenoxide compound contains at least one hydride or hydrocarbyl ligand, activation can be achieved by removal of formal anionic or neutral ligands, of higher binding affinity than the unsaturated monomer. This removal, also called abstraction, process may have a kinetic rate that is first-order or non-first order with respect to the activator. Activators that remove formal anonic ligands are termed ionizing activators. Activators that remove formal neutral ligands are termed non-ionizing activators. Activators are typically strong Lewis-acids which may play either the role of ionizing or non-ionizing activator.

When the E-phenoxide compound does not contain at least one hydride or hydrocarbyl ligands, then activation may be a one step or multi step process. A step in this process includes coordinating a hydride or hydrocarbyl group to the metal compound. A separate activation step is removal of formal anionic or neutral ligands of higher binding affinity than the unsaturated monomer. These activation steps may occur in series or in parallel. These steps may occur in the presence of olefin. These steps may occur prior to exposure to olefin. More than one sequence of activation steps is possible to achieve activation.

The activator may also act to coordinate a hydride or hydrocarbyl group to the metal compound, containing at least one E-Phenoxide ligand and one formal neutral ligand. When the E-phenoxide compound does not contain at least one hydride or hydrocarbyl ligands but does contain at least one functional group ligand, activation may be effected by substitution of the functional group with a hydride, hydrocarbyl or substituted hydrocarbyl group. This substitution may be effected with appropriate hydride or alkyl reagents of group 1, 2, 12, 13 elements as is known in the art. To achieve activation, it may be necessary to also remove formal anionic or neutral ligands of higher binding affinity than the unsaturated monomer.

Alumoxane and aluminum alkyl activators are capable of alkylation and abstraction activation.

The activator may also act to coordinate a hydride or hydrocarbyl group to the metal compound, containing at least one E-Phenoxide ligand and one formal neutral ligand. If the E-phenoxide compound does not contain formal anionic ligands, then a hydride, hydrocarbyl or substituted hydrocarbyl may be coordinated to a metal using electrophilic proton or alkyl transfer reagents represented by H.sup.+(LB).sub.nA.sup.-, (R.sup.9).sup.+(LB).sub.nA.sup.-. R.sup.9 is a hydrocarbyl or a substituted hydrocarbyl; LB is a Lewis-base, n=0, 1 or 2. Non-limiting examples of preferred Lewis-bases are diethyl ether, dimethyl ether, ethanol, methanol, water, acetonitrile, N,N-dimethylaniline. A.sup.- is an anion preferably a substituted hydrocarbon, a functional group, or a non-coordinating anion. Non-limiting examples of A.sup.- include halides, carboxylates, phosphates, sulfates, sulfonates, borates, aluminates, alkoxides, thioalkoxides, anionic substituted hydrocarbons, anionic metal complexes.

A. Alumoxane and Aluminum Alkyl Activators

In one embodiment, one or more alumoxanes are utilized as an activator in the catalyst composition of the invention. Alumoxanes, sometimes called aluminoxanes in the art, are generally oligomeric compounds containing --Al(R)--O-- subunits, where R is an alkyl group. Examples of alumoxanes include methylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxane and isobutylalumoxane. Alkylalumoxanes and modified alkylalumoxanes are suitable as catalyst activators, particularly when the abstractable ligand is a halide. Mixtures of different alumoxanes and modified alumoxanes may also be used. For further descriptions, see U.S. Pat. Nos. 4,665,208, 4,952,540, 5,041,584, 5,091,352, 5,206,199, 5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,329,032, 5,248,801, 5,235,081, 5,157,137, 5,103,031 and EP 0 561 476 A1, EP0 279 586B1, EP0 516 476A, EP0 594 218A1 and WO94/10180.

When the activator is an alumoxane (modified or unmodified), some embodiments select the maximum amount of activator at a 5000-fold molar excess Al/M over the catalyst precursor (per metal catalytic site). The minimum activator-to-catalyst-precursor is typically a 1:1 molar ratio.

Alumoxanes may be produced by the hydrolysis of the respective trialkylaluminum compound. MMAO may be produced by the hydrolysis of trimethylaluminum and a higher trialkylaluminum such as triisobutylaluminum. MMAO's are generally more soluble in aliphatic solvents and more stable during storage. There are a variety of methods for preparing alumoxane and modified alumoxanes, non-limiting examples of which are described in U.S. Pat. Nos. 4,665,208, 4,952,540, 5,091,352, 5,206,199, 5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,308,815, 5,329,032, 5,248,801, 5,235,081, 5,157,137, 5,103,031, 5,391,793, 5,391,529, 5,693,838, 5,731,253, 5,731,451, 5,744,656, 5,847,177, 5,854,166, 5,856,256 and 5,939,346 and European publications EP-A-0 561 476, EP-B1-0 279 586, EP-A-0 594-218 and EP-B1-0 586 665, and PCT publications WO 94/10180 and WO 99/15534, all of which are herein fully incorporated by reference. It may be preferable to use a visually clear methylalumoxane. A cloudy or gelled alumoxane can be filtered to produce a clear solution or clear alumoxane can be decanted from the cloudy solution. Another preferred alumoxane is a modified methyl alumoxane (MMAO) cocatalyst type 3A (commercially available from Akzo Chemicals, Inc. under the trade name Modified Methylalumoxane type 3A, covered under patent number U.S. Pat. No. 5,041,584).

Aluminum alkyl or organoaluminum compounds which may be utilized as activators (or scavengers) include trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum and the like.

B. Ionizing Activators

It is within the scope of this invention to use an ionizing or stoichiometric activator, neutral or ionic, such as tri (n-butyl) ammonium tetrakis (pentafluorophenyl) boron, a trisperfluorophenyl boron metalloid precursor or a trisperfluoronaphtyl boron metalloid precursor, polyhalogenated heteroborane anions (WO 98/43983), boric acid (U.S. Pat. No. 5,942,459) or combination thereof. It is also within the scope of this invention to use neutral or ionic activators alone or in combination with alumoxane or modified alumoxane activators.

Examples of neutral stoichiometric activator