WO2007076231A2

WO2007076231A2 - Bridged phenol-heterocyclic ligands, metal complexes, and their uses as catalysts

Info

Publication number: WO2007076231A2
Application number: PCT/US2006/061790
Authority: WO
Inventors: Lily Ackerman; Gary M. Diamond; James A.W. Shoemaker; Cynthia Micklatcher; Xiaohong Bei; James Longmire
Original assignee: Symyx Technologies, Inc.
Priority date: 2005-12-16
Filing date: 2006-12-07
Publication date: 2007-07-05
Also published as: WO2007076231A3

Abstract

Ligands, compositions, and metal-ligand complexes that incorporate bridged phenol-heterocyclic compounds are disclosed that are useful in the catalysis of transformations such as the polymerization of monomers into polymers.

Description

BRIDGED PHENOL-HETEROCYCLIC LIGANDS, METAL COMPLEXES, AND THEIR USES AS CATALYSTS

TECHNICAL FIELD

[001] The present invention relates to ligands, ligand-metal compositions, complexes, and catalysts useful in the polymerization of olefins and other transformations.

BACKGROUND OF THE INVENTION

[002] Ancillary ligand-metal coordination complexes are prepared by combining an ancillary ligand with a suitable metal compound or metal precursor in a suitable solvent at a suitable temperature. Certain known ancillary ligand-metal complexes and compositions are catalysts for reactions such as oxidation, reduction, hydrogenation and other transformations. One use for ancillary ligand-metal complexes and compositions is in the field of polymerization catalysis, where the ancillary ligand offers opportunities to modify the electronic and/or steric environment surrounding an active metal center. This allows the ancillary ligand to assist in the creation of possibly different polymers. What is needed is discovery of novel ancillary ligand-metal complexes and compositions that meet the specific, commercial needs of the polyolefin industry. [003] An extensive body of scientific literature examines catalyst structures, mechanism and polymers prepared by catalysts. See, e.g., G. W. Coates, "Precise Control of Polyolefin Stereochemistry Using Single-Site Metal Catalysts," Chem. Rev. 2000, 100, 1223-1252; "The Search for New-Generation Olefin Polymerization Catalysts: Life beyond Metallocenes", Gibson, et al., Angew. Chem. Int. Ed. 1999, 38, 428-447; Organometallics 1999, 18, 3649-3670; and "Advances in Non-Metallocene Olefin Polymerization Catalysts", Gibson, et al., Chem Rev. 2003, 103, 283-315. Various references also publish the results of experiments in polyolefin catalysis. See, e.g., EP 0 874005, EP 0 950 667, WO 2003/091262 and U.S. Patent 6,309,997. See also Cuomo, C. et al., Macromolecules, 2004, 7469-7476.

[004] One area of interest in polyolefin catalysis are novel catalysts that are highly active to produce a polymer that either highly incorporates a co-monomer or incorporates almost no co-monomer even in the presence of the co-monomer. Therefore, a need remains for new polyolefin catalysts in general, and in particular a need remains for highly active catalysts that incorporate a comonomer very well or not well at all. SUMMARY OF THE INVENTION

[005] The invention features ligands, compositions and metal complexes that are useful in catalysts for olefin polymerization and other transformations, as well as methods for preparing the ligands and for using the compositions or complexes in catalytic transformations such as olefin polymerization. In general, the ligands have a bridged phenol-heterocyclic structure. Catalysts according to the invention can be provided by compositions including a ligand, a metal precursor, and optionally an activator, combination of activators, or an activator technique. Alternatively, catalysts can be provided by metal-ligand complexes and optionally may additionally include an activator, combination of activators or activator technique. [006] hi general, in one aspect, the invention provides compositions of matter, including ligands, compositions and metal-ligand complexes, that include a compound characterized by the formula:

wherein X¹ is N or C, X² is O, S, N(R⁵V or CR⁵, X³ is O, S, N(R⁶)_n- or CR⁶, X⁴ is O, S, N(R⁷V- or CR⁷, wherein each n', n", and n'" are each independently 0 or 1, provided that the heteroatom containing ring system is heteroaromatic; X⁵ is N or C, X⁶ is O, S, N(R⁵)_n> or CR⁵, X⁷ is O, S, N(R⁶V- or CR⁶, X^s is O, S, N(R⁷V_" or CR⁷, wherein each n', n", and n'" are each independently 0 or 1, provided that the heteroatom containing ring system is heteroaromatic; B is a bridging group linking the heteroaromatic rings and having up to 50 atoms hi the bridge not counting hydrogen atoms, provided that the bridging group links one of X², X³, or X⁴ to one of X⁶, X⁷, or X⁸; each R¹, R², R³, R⁴, R⁵, R⁶, and R⁷ are the same or different from each other and are independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloaikyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, halo, silyl, boryl, phosphino, amino, thioalkyl, thioaryl, and combinations thereof, optionally two or more of R¹, R², R³, and R⁴ on any one ring may be joined to form a fused ring system having up to 50 atoms, not counting hydrogen atoms; and optionally two or more of R⁵, R⁶, and R⁷ on any one ring may be joined to form a fused ring system having up to 50 atoms, not counting hydrogen atoms; M is a metal selected from the group consisting of groups 3 through 6 of the Periodic Table of Elements and lanthanides; each L is independently selected from the group consisting of hydrogen, halogen, optionally substituted alkyl, heteroalkyl, allyl, diene, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, aryl, heteroaryl, alkoxy, aryloxy, boryl, silyl, amino, phosphino, ether, thioether, phosphine, amine, carboxylate, alkylthio, arylthio, 1 ,3-dionate, oxalate, carbonate, nitrate, sulphate, and combinations thereof; and m" is 0, 1, 2, 3, or 4. [007] This compound can have a variety of different bridging groups. Additional aspects include those where the compound is symmetrical or asymmetrical, with such asymmetry coming from either the R groups or from the selection of the atoms in the heteroaromatic rings (i.e., X^]-X⁸). In addition, the dotted line bond shown between the N atoms and the metal M can be present or absent and can alternate between being present and absent, giving it fluxional character.

[008] Compounds shown above are prepared from the combination of a ligand with a metal precursor compound. The compounds or complexes are typically activated for polymerization activity.

[009] In general, in another aspect, the invention provides catalytic methods. In the methods, one or more reagents is reacted in the presence of a catalyst comprising a composition or complex as described above, and optionally one or more activators, under conditions sufficient to yield one or more reaction products.

[010] In general, in another aspect, the invention provides polymerization processes that employ the composition or complexes of the invention, optionally in the presence of at least one activator. In particular embodiments, the activator can include an ion forming activator and, optionally, a group 13 reagent. The activator can include an alumoxane.

[011] In general, in another aspect, the invention provides a process for the polymerization of an alpha-olefin. According to the process, at least one alpha-olefin is polymerized in the presence of a catalyst formed from a composition or complex of the invention, optionally in the presence of one or more activators, under polymerization conditions sufficient to form a substantially stereoregular polymer. In another aspect, the catalysts of this invention arc useful for polymerizing ethylene with low co-monomer incorporation, even in the presence of the co-monomer. This aspect is particularly useful for bi-modal product distributions, if desired. In another aspect, the catalysts of this invention are useful for the polymerization of vinylidene monomers, such as styrene to homopolystyrene, for example.

[012] In general, in another aspect, the invention provides a process for polymerizing ethylene and at least one alpha-olefϊn. According to the process, ethylene is polymerized in the presence of at least one alpha-olefin in the presence of a catalyst formed from a composition or complex of the invention, optionally in the presence of one or more activators.

[013] Particular embodiments can include one or more of the following features. The at least one alpha-olefin can include propylene, 1-butene, 1-hexene, 1-octene, 1-decene, or styrene. The process can be a solution process, and can be operated under polymerization conditions that include a temperature of at least 100⁰C, or at least 125°C. Also the process can be slurry or gas phase polymerization, using supported catalyst, at temperatures between 60°C and 110°C.

[014] In general, in another aspect, the invention provides a process for polymerizing at least one monomer including providing a reactor with reactor contents including at least one polymerizable monomer and a composition or complex of the invention, and subjecting the reactor contents to polymerization conditions. In particular embodiments, the at least one polymerizable monomer can include ethylene and propylene, ethylene and 1-hexene, ethylene and 1-butene, 1-octene, 1-decene, ethylene and styrene, ethylene and a cyclic alkene, ethylene and a diene, or ethylene, propylene, and a diene selected from the group consisting of ethylidenenorbornene, dicyclopentadiene, and 1,4- hexadiene.

[015] The invention can be implemented to provide one or more of the following advantages. The ligands, compositions, complexes and polymerization methods of the invention can be used to provide catalysts exhibiting enhanced activity. Catalysts incorporating the ligands, compositions and/or complexes can be used to catalyze a variety of transformations, such as olefin oligomerization (specifically dimerization, trimerization and tetramerization) or polymerization. By selecting an appropriate ligand and metal, compositions and/or complexes can be obtained to provide for desired properties in the resulting product. Thus, polymers produced using the ligands, compositions, complexes, and methods of the invention can exhibit higher (or lower) melting points, higher (or lower) molecular weights, and/or higher (or lower) polydispersities, than polymers produced using prior known catalysts. In some embodiments, polymer products having bi- or multi-modal distributions of product composition and/or molecular weight can be obtained by selecting a single catalyst precursor and activating it under certain conditions. Catalysts incorporating the ligands, compositions and/or complexes can be used according to the polymerization methods of the invention to produce polymers under commercially desirable polymerization conditions. Catalysts incorporating the ligands, compositions and complexes of the invention can exhibit catalytic activity at higher temperatures than prior known catalysts. Copolymerization processes (e.g., ethylene/α-olefin copolymerizations) using the ligands, compositions and complexes of the invention can exhibit higher (or lower) comonomer incorporation than processes involving prior known catalysts. Chiral compositions and/or complexes according to the invention can be used to catalyze stereoselective, enantioselective or diastereoselective transformations.

BRIEF DESCRIPTION OF THE DRAWINGS

[016] Figure 1 is a list of certain ligands and metal complexes, in accord with the invention herein.

DETAILED DESCRIPTION

[017] The invention provides ligands, compositions and complexes that are useful as catalysts for a variety of transformations, including olefin polymerization reactions. [018] As used herein, the phrase "characterized by the formula" is not intended to be limiting and is used in the same way that "comprising" is commonly used. The term "independently selected" is used herein to indicate that the groups in question — e.g., R¹, R², R³, R⁴, R⁵, etc. -- can be identical or different (e.g., R¹, R², R³, R⁴, R⁵, etc. may all be substituted alkyls, or R¹ and R² may be a substituted alkyl and R³ may be an aryl, etc.). Use of the singular includes use of the plural and vice versa (e.g., a hexane solvent, includes hexanes). For R groups, any particular R group may be the same or different from commonly named R group; for example, two R¹ groups may be in a particular formula and the two R¹ groups may be the same or different. A named R group will generally have the structure that is recognized in the art as corresponding to R groups having that name. The terms "compound" and "complex" are generally used interchangeably in this specification, but those of skill in the art may recognize certain compounds as complexes and vice versa. For the purposes of illustration, representative certain groups are defined herein. These definitions are intended to supplement and illustrate, not preclude, the definitions known to those of skill in the art. [019] "Optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where the event or circumstance occurs and instances where it does not. For example, the phrase "optionally substituted hydrocarbyl" means that a hydrocarbyl moiety may or may not be substituted and that the description includes both unsubstituted hydrocarbyl and hydrocarbyl where there is substitution.

[020] The term "substituted" as in "substituted hydrocarbyl," "substituted aryl," "substituted alkyl," and the like, means that in the group in question (i.e., the hydrocarbyl, alkyl, aryl or other moiety that follows the term), at least one hydrogen atom bound to a carbon atom is replaced with one or more substituent groups such as hydroxy, alkoxy, alkylthio, phosphino, amino, halo, silyl, and the like. When the term "substituted" introduces a list of possible substituted groups, it is intended that the term apply to every member of that group. That is, the phrase "substituted alkyl, alkenyl and alkynyl" is to be interpreted as "substituted alkyl, substituted alkenyl and substituted alkynyl." Similarly, "optionally substituted alkyl, alkenyl and alkynyl" is to be interpreted as "optionally substituted alkyl, optionally substituted alkenyl and optionally substituted alkynyl."

[021] The term "saturated" refers to the lack of double and triple bonds between atoms of a radical group such as ethyl, cyclohexyl, pyrrolidinyl, and the like. The term "unsaturated" refers to the presence of one or more double and triple bonds between atoms of a radical group such as vinyl, allyl, acetylide, oxazolinyl, cyclohexenyl, acetyl and the like, and specifically includes alkenyl and alkynyl groups, as well as groups in which double bonds are delocalized, as in aryl and heteroaryl groups as defined below. [022] The terms "cyclo" and "cyclic" are used herein to refer to saturated or unsaturated radicals containing a single ring or multiple condensed rings. Suitable cyclic moieties include, for example, cyclopentyl, cyclohexyl, cyclooctenyl, bicyclooctyl, phenyl, napthyl, pyrrolyl, furyl, thiophenyl, imidazolyl, and the like, hi particular embodiments, cyclic moieties include between 3 and 200 atoms other than hydrogen, between 3 and 50 atoms other than hydrogen or between 3 and 20 atoms other than hydrogen.

[023] The term "hydrocarbyl" refers to hydrocarbyl radicals containing 1 to about 50 carbon atoms, specifically 1 to about 24 carbon atoms, most specifically 1 to about 16 carbon atoms, including branched or unbranched, cyclic or acyclic, saturated or unsaturated species, such as alkyl groups, alkenyl groups, aryl groups, and the like. [024] The term "alkyl" as used herein refers to a branched or unbranched saturated hydrocarbon group typically although not necessarily containing 1 to about 50 carbon atoms, such as methyl, ethyl, ^-propyl, isopropyl, H-butyl, isobutyl, sec-butyl, /f-butyl, octyl, decyl, and the like, as well as cycloalkyl groups such as cyclopentyl, cyclohexyl and the like. Generally, although again not necessarily, alkyl groups herein may contain 1 to about 20 carbon atoms.

[025] The term "alkenyl" as used herein refers to a branched or unbranched, cyclic or acyclic hydrocarbon group typically although not necessarily containing 2 to about 50 carbon atoms and at least one double bond, such as ethenyl, «-propenyl, isopropenyl, n- butenyl, isobutenyl, octenyl, decenyl, and the like. Generally, although again not necessarily, alkenyl groups herein contain 2 to about 20 carbon atoms. [026] The term "alkynyl" as used herein refers to a branched or unbranched, cyclic or acyclic hydrocarbon group typically although not necessarily containing 2 to about 50 carbon atoms and at least one triple bond, such as ethynyl, «-propynyl, isopropynyl, n- butynyl, isobutynyl, octynyl, decynyl, and the like. Generally, although again not necessarily, alkynyl groups herein may have 2 to about 20 carbon atoms. [027] The term "aromatic" is used in its usual sense, including unsaturation that is essentially delocalized across several bonds around a ring. The term "aryl" as used herein refers to a group containing an aromatic ring. Aryl groups herein include groups containing a single aromatic ring or multiple aromatic rings that are fused together, linked covalently, or linked to a common group such as a methylene or ethylene moiety. More specific aryl groups contain one aromatic ring or two or three fused or linked aromatic rings, e.g., phenyl, naphthyl, biphenyl, anthracenyl, or phenanthrenyl. hi particular embodiments, aryl substituents include 1 to about 200 atoms other than hydrogen, typically 1 to about 50 atoms other than hydrogen, and specifically 1 to about 20 atoms other than hydrogen. In some embodiments herein, multi-ring moieties are substituents and in such embodiments the multi-ring moiety can be attached at an appropriate atom. For example, "naphthyl" can be 1-naphthyl or 2-naphthyl; "anthracenyl" can be 1-anthracenyl, 2-anthracenyl or 9-anthracenyl; and "phenanthrenyl" can be 1 -phenanthrenyl, 2-phenanthrenyl, 3-phenanthrenyl, 4-phenanthrenyl or 9- phenanthrenyl.

[028] The term "alkoxy" as used herein intends an alkyl group bound through a single, terminal ether linkage; that is, an "alkoxy" group may be represented as -O-alkyl where alkyl is as defined above. The term "aryloxy" is used in a similar fashion, and may be represented as -O-aryl, with aryl as defined below. The term "hydroxy" refers to —OH. [029] Similarly, the term "alkylthio" as used herein intends an alkyl group bound through a single, terminal thioether linkage; that is, an "alkylthio" group may be represented as -S-alkyl where alkyl is as defined above. The term "arylthio" is used similarly, and may be represented as — S-aryl, with aryl as defined below. The term "mercapto" refers to -SH.

[030] The terms "halo" and "halogen" are used in the conventional sense to refer to a chloro, bromo, fluoro or iodo radical.

[031] The terms "heterocycle" and "heterocyclic" refer to a cyclic radical, including ring-fused systems, including heteroaryl groups as defined below, in which one or more carbon atoms in a ring is replaced with a heteroatom - that is, an atom other than carbon, such as nitrogen, oxygen, sulfur, phosphorus, boron or silicon. Heterocycles and heterocyclic groups include saturated and unsaturated moieties, including heteroaryl groups as defined below. Specific examples of heterocycles include pyrrolidine, pyrroline, furan, tetrahydrofuran, thiophene, imidazole, oxazole, thiazole, indole, and the like, including any isomers of these. Additional heterocycles are described, for example, in Alan R. Katritzky, Handbook of Heterocyclic Chemistry , Pergammon Press, 1985, and in Comprehensive Heterocyclic Chemistry, A.R. Katritzky et al., eds, Elsevier, 2d. ed., 1996. The term "metallocycle" refers to a heterocycle in which one or more of the heteroatoms in the ring or rings is a metal.

[032] The term "heteroaryl" refers to an aryl radical that includes one or more heteroatoms in the aromatic ring. Specific heteroaryl groups include groups containing heteroaromatic rings such as thiophene, pyridine, pyrazine, isoxazole, pyrazole, pyrrole, furan, thiazole, oxazole, imidazole, isothiazole, oxadiazole, triazole, and benzo-fused analogues of these rings, such as indole, carbazole, benzofuran, benzothiophene, benzimidiazole, benzthiazole, benzoxazoles, indazole and the like and isomers thereof, e.g., reverse isomers.

[033] More generally, the modifiers "hetero" and "heteroatom-containing", as in "heteroalkyl" or "heteroatom-containing hydrocarbyl group" refer to a molecule or molecular fragment in which one or more carbon atoms is replaced with a heteroatom. Thus, for example, the term "heteroalkyl" refers to an alkyl substituent that is heteroatom-containing. When the term "heteroatom-containing" introduces a list of possible heteroatom-containing groups, it is intended that the term apply to every member of that group. That is, the phrase "heteroatom-containing alkyl, alkenyl and alkynyl" is to be interpreted as "heteroatom-containing alkyl, heteroatom-containing alkenyl and heteroatom-containing alkynyl."

[034] By "divalent" as in "divalent hydrocarbyl", "divalent alkyl", "divalent aryl" and the like, is meant that the hydrocarbyl, alkyl, aryl or other moiety is bonded at two points to atoms, molecules or moieties with the two bonding points being covalent bonds. [035] As used herein the term "silyl" refers to the -SiZ¹Z²Z³ radical, where each of Z¹ , Z², and Z³ is independently selected from the group consisting of hydrogen and optionally substituted alkyl, alkenyl, alkynyl, heteroatom-containing alkyl, heteroatom- containing alkenyl, heteroatom-containing alkynyl, aryl, heteroaryl, alkoxy, aryloxy, amino, silyl and combinations thereof.

[036] As used herein the term "boryl" refers to the -BZ¹Z² group, where each of Z¹ and Z² is as defined above. As used herein, the term "phosphino" refers to the group -PZ¹Z², where each of Z¹ and Z² is as defined above. As used herein, the term "phosphine" refers to the group ^Z¹Z²Z³, where each of Z¹, Z³ and Z² is as defined above. The term "amino" is used herein to refer to the group -NZ¹Z², where each of Z¹ and Z² is as defined above. The term "amine" is used herein to refer to the group :NZ^XZ²Z³, where each of Z¹, Z² and Z³ is as defined above.

[037] Other abbreviations used herein include: "Cbz" to refer to N-carbazole; "¹Pr" to refer to isopropyl; "¹Bu" to refer to tert-butyl; "Me" to refer to methyl; "Et" to refer to ethyl; "Ph" to refer to phenyl; "Mes" to refer to mesityl (2,4,6-trimethyl phenyl); "TFA" to refer to trifiuoroacetate and "THF" to refer to tetrahydrofuran. [038] The ligands according to the invention can be characterized broadly as bridged ligands having two phenols and two heterocyclic or substituted heterocyclic groups. In some embodiments, the ligands of the invention can be characterized by the following structure (I):

wherein each X¹ is N or C, X² is O, S, N(R⁵)_n- or CR⁵, X³ is O, S, N(R⁶)_n- or CR⁶, X⁴ is

O, S, N(R⁷V_" or CR⁷, wherein each n\ n", and n'" are each independently O or 1, provided that the heteroatom containing ring system is heteroaromatic.

[039] Also in formula (I), X⁵ is N or C₅ X⁶ is O, S, N(R⁵)_n. or CR⁵, X⁷ is O, S, N(R⁶)_n» or CR⁶, X⁸ is O, S, N(R⁷)_n- or CR⁷, wherein each n', n", and n'" are each independently O or 1 , provided that the heteroatom containing ring system is heteroaromatic.

[040] Also in formula (I), B is a bridging group linking the heteroaromatic rings and having up to 50 atoms in the bridge not counting hydrogen atoms, provided that the bridging group links one of X², X³, or X⁴ to one of X⁶, X⁷, or X⁸. As a general matter, when B is bonded to an X, the corresponding R group is not present on the X.

[041] Also in formula (I), each R¹, R², R³, R⁴, R⁵, R⁶, and R⁷ are the same or different from each other and are independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, halo, silyl, boryl, phosphino, amino, thioalkyl, thioaryl, and combinations thereof, optionally two or more of R¹, R², R³, and

R⁴ on any one ring may be joined to form a fused ring system having up to 50 atoms, not counting hydrogen atoms; and optionally two or more of R⁵, R⁶, and R⁷ on any one ring may be joined to form a fused ring system having up to 50 atoms, not counting hydrogen atoms.

[042] In certain embodiments, R¹ is selected from the group consisting of optionally substituted alkyl, heteroalkyl, aryl and heteroaryl; more specifically, selected from the group consisting of alkyl, substituted alkyl, naphthyl, substituted naphthyl, N-carbazolyl, substituted N-carbazolyl, phenyl, substituted phenyl, indolyl, substituted indolyl, adamantyl, substituted adamantyl, thiophenyl, substituted thiophenyl, benzofuranyl, substituted benzofuranyl, benzothiophenyl and substituted benzothiophenyl. Also in certain embodiments, R¹ is not hydrogen.

[043] Generally, the ligand of formula (I) is either symmetric or asymmetric across the bridging group B. When asymmetric, the asymmetry can arise from the selection of the various R groups or from the selection of the atoms in the backbone of the ligand. hi some embodiments, the asymmetrical ligand is a result of the selection of the C, N, O or S atom in the heterocyclic ring, at least, either X¹ and X⁵ are different or X² and X⁶ are different or X³ and X⁷ are different or X⁴ and X⁸ are different.

[044] In other aspects, the bridging group — B- is selected from the group consisting of divalent, optionally substituted alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, aryl, heteroaryl and silyl. In still other aspects, the bridging group -B- is substituted with one or more optionally substituted hydrocarbyl or heteroatom-containing hydrocarbyl groups. In some aspects, the bridging group contains one or more cliiral centers and may or may not be enantiomerically or diastereoically pure. [045] In still other aspects, -B- is represented by the general formula — (Q"R⁴⁰2_-Z")z_' — wherein each Q" is independently either carbon or silicon and wherein each R⁴⁰ substituent is independently selected from the group consisting of hydrogen and optionally substituted hydrocarbyl and heteroatom containing hydrocarbyl, wherein two or more R⁴⁰ substituents are optionally joined into a ring structure having from 3 to 50 atoms in the ring structure not counting hydrogen atoms; z' is an integer from 1 to 20; and z" is 0, I or 2. [046] In other aspects, -B- is selected from the group consisting of:

wherein each Q is independently selected from the group consisting of carbon and silicon, each R⁶⁰ is independently selected from the group consisting of hydrogen and optionally substituted hydrocarbyl and heteroatom containing hydrocarbyl, provided that at least one R⁶⁰ substituent is not hydrogen, wherein the R⁶⁰ substituents are optionally joined into a ring structure having from 3 to 50 atoms in the ring structure not counting hydrogen atoms, and m' is 0, 1, or 2. Particular aspects include where -B- is selected from the group consisting Of-(CH₂)-, -(CH₂)₂-, -(CH₂)₃-,-(CH₂)4-, -(CH₂)₅-, -(CH₂)₆-, -(CH₂)J-, -(CH₂)_S-, -(CH(CH₃))-, -(CH(CH₃))₂-, -(C(CH₃),)-, -(C(CH₃)₂)₂-, -(C(CH₃)₂)₃-, -CH₂CH(CH₃)CH₂-, -CH₂C(CHs)₂CH₂- -CH₂CH(C₆H₅)CH₂-, -CH(CH₃)CH₂CH(CH₃)- -CH(C₂H₅)CH₂CH(C₂H₅)-, -CH(CH₃)CH₂CH₂CH(CH3)- -CH(C₆H₅)CH₂CH(C₆H₅)- — CH(C₆H₅)CH₂CH(C₆H₅)- -(C₆H₄)CH₂CH₂(C₆H₄)- -(C₆H₄)CH₂CH₂CH₂(C₆H₄K -(C₆H₄)CH₂CH₂CH₂CH₂(C₆H₄)-

[047] In still other aspects, -B- is represented by the formula

where (Q"R⁴⁰ _2-Z")z_' is defined above and wherein each R^δυ substituent is independently selected from the group consisting of hydrogen, halo and optionally substituted hydrocarbyl and heteroatom containing hydrocarbyl, wherein two or more R⁸⁰ substituents are optionally joined into a ring structure having from 3 to 50 atoms in the ring structure not counting hydrogen atoms, and a is 0, 1, 2 or 3; more specifically, each R⁸⁰ substituent are the same or different from each other and are independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryi, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, halo, silyl, boryl, phosphino, amino, thioalkyl, thioaryl, and combinations thereof, optionally two or more of R⁸⁰ groups on any one ring may be joined to form a fused ring system having up to 50 atoms, not counting hydrogen atoms. [048] In preferred embodiments, the bridging group is attached to either the X³, X⁴, X⁷ or X⁸ atom. Thus, the ligands include:

[049] Certain combinations of atoms in the rings of the heterocyclic rings are preferred. The following Table 1 shows combinations that are preferred for X¹ through X⁴ : Table 1

X¹ X² X³ X⁴

C O N C

C N O C

C N C C

C S C C

C C S C

N C C C

C C C N

N N C C

N N C N

N N N C

C C N C

C O C C

C C O C

In Table 1 , the R groups axe not included, but are as recited herein when the appropriate atom is selected for a particular embodiment.

[050] The following Table 2 shows combinations that are preferred for X⁵ through X⁸:

Table 2

X⁵ X⁶ X⁷ X⁸

C O N C

C N O C

C N C C

C S C C

C C S C

N C C C

C C C N

N N C C

N N C N

N N N C C C N C

C O C C

C C O C

In Table 2, the R groups are not included, but are as recited herein when the appropriate atom is selected for a particular embodiment. Any of the combinations in Table 1 may be matched with any of the combinations in Table 2, giving over 160 combinations. Not all embodiments of the formulae herein will comply with the bonding shown when considering all the combinations listed in Tables 1 and 2, and thus the combinations in Tables 1 and 2 should be chosen by those of skill in the art such that the heteroaromatic ring is not charged (e.g., avoid a quaternary nitrogen atom) and is aromatic. [051] In formulae (I), (Ia), (Ib), etc. and those presented throughout this specification, the presence of one solid line and one dashed line between any pair of atoms is intended to indicate that the bond in question may be a single bond or a double bond, or a bond with bond order intermediate between single and double, such as the delocalized bonding in an aromatic ring.

[052] It should be understood that in the compounds identified in various formulae that the substituent R¹ through R¹ ' , if present in the molecule, and not specifically identified, are as defined throughout the specification.

[053] The choice of particular heterocyclic ligand can have a strong influence on the catalysis of particular transformations. Thus, the choice of substituent in the ligands of the invention when incorporated in a polymerization catalyst can affect catalyst activity, thermal stability, molecular weight of the product polymer, or the degree and/or kind of stereo- or regioerrors, as well as other factors known to be significant in the production of various polymers.

[054] The ligands of the invention can be prepared using known procedures, such as those described, for example, in March, Advanced Organic Chemistry, Wiley, New York 1992 (4^th Ed.), and in Katritzky et al., Comprehensive Heterocyclic Chemistry, Elsevier, New York 1984 (1^st Ed.) & 1996 (2^nd Ed.)- Specifically, in some embodiments the ligands of the invention can be prepared according to the general procedures that follow. [055] Once the desired ligand is formed, it can be combined with a metal atom, ion, compound or other metal precursor compound, and in some embodiments the present invention encompasses compositions that include any of the above-mentioned ligands in combination with an appropriate metal precursor and an optional activator. For example, in some embodiments, the metal precursor can be an activated metal precursor, which refers to a metal precursor (described below) that has been combined or reacted with an activator (described below) prior to combination or reaction with the ancillary ligand. As noted above, in one aspect the invention provides compositions that include such combinations of ligand and metal atom, ion, compound or precursor. In some applications, the ligands are combined with a metal compound or precursor and the product of such combination is not determined, if a product forms. For example, the ligand may be added to a reaction vessel at the same time as the metal or metal precursor compound along with the reactants, activators, scavengers, etc. Additionally, the ligand can be modified prior to addition to or after the addition of the metal precursor, e.g. through a deprotonation reaction or some other modification.

[056] In general, the metal precursor compounds can be characterized by the general formula M(L)_m where M is a metal selected from the group consisting of groups 3-6 and lanthanides of the periodic table of elements and m is 1, 2, 3, 4, 5, or 6. Thus, in particular embodiments M can be selected from scandium, yttrium, titanium, zirconium, hamium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. Each L is a ligand independently selected from the group consisting of hydrogen, halogen, optionally substituted alkyl, heteroalkyl, allyl, diene, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, aryl, heteroaryl, alkoxy, aryloxy, boryl, silyl, amino, phosphino, ether, thioether, phosphine, amine, carboxylate, alkylthio, arylthio, 1,3-dionate, oxalate, carbonate, nitrate, sulphate, and combinations thereof. Optionally, two or more L groups are joined into a ring structure. One or more of the ligands L may be ionically bonded to the metal M and, for example, L may be a non-coordinated or loosely coordinated or weakly coordinated anion (e.g., L may be selected from the group consisting of those anions described below in the conjunction with the activators). (See Marks et al., Chem. Rev. 2000, 100, 1391-1434, for a detailed discussion of these weak interactions.) The metal precursors may be monomeric, dimeric or higher orders thereof. In particular embodiments, the metal precursor includes a metal selected from Ti₅ Zr, or Hf. In more specific embodiments, the metal precursor includes a metal selected from Zr and Hf. [057] Specific examples of suitable titanium, hafnium and zirconium precursors include, but are not limited to TiCl₄, Ti(CH₂Ph)₄, Ti(CH₂CMc₃)₄, Ti(CH₂SiMe₃)₄, Ti(CH₂Ph)₃Cl₅ Ti(CH₂CMe₃)SCl, Ti(CH₂SiMe_S)₃Cl₁ Ti(CH₂Ph)₂Cl₂, Ti(CH₂CMe₃)₂Cl₂, Ti(CH₂SiMe₃)₂Cl₂, Ti(NMe₂)₄, Ti(NEt₂)* Ti(O-¹Pr)₄, and Ti(N(SiMe₃)₂)₂Cl₂; HfCl₄, Hf(CH₂Ph)₄, Hf(CH₂CMe₃)₄, Hf(CH₂SiMe₃)₄, Hf(CH₂Ph)₃Cl, Hf(CH₂CMe₃)₃Cl, Hf(CH₂SiMe₃)₃Cl, Hf(CH₂Ph)₂Cl₂, Hf(CH₂CMe₃)₂Cl₂, Hf(CH₂S iMe₃)₂Cl₂,Hf(NMe₂)₄, Hf(NEt₂)₄, and Hf(N(SiMe₃)₂)₂Gl₂, Hf(N(SiMe₃)CH₂CH₂CH₂N(SiMe₃))Cl₂, Hf(N(Ph)CH₂CH₂CH₂N(Ph))Cl₂, ZrCl₄, Zr(CH₂Ph)₄, Zr(CH₂CMe₃)₄, Zr(CH₂SiMe₃)* Zr(CH₂Ph)₃Cl₃ Zr(CH₂CMe₃)₃Cl, Zr(CH₂SiMe₃)₃Cl, Zr(CH₂Ph)₂Cl₂, Zr(CH₂CMe₃)₂Cl₂, Zr(CH₂SiMe₃)₂Cl₂,Zr(NMe₂)₄, Zr(NEt₂)₄, Zr(NMe₂)₂Cl₂, Zr(NEt₂)₂Cl₂, Zr(N(SiMe₃)₂)₂Cl₂, Zr(N(SiMe₃)CH₂ CH₂CH₂N(SiMe₃))Cl₂, and

Zr(N(Ph)CH₂CH₂CH₂N(Ph))Cl₂. Lewis base adducts of these examples are also suitable as metal precursors, for example, ethers, amines, thioethers, phosphines and the like are suitable as Lewis bases. Specific examples include HfCl₄(THF)₂, HfCl₄(SMe₂)2 and Hf(CH₂Ph)₂Cl₂(OEt₂). Activated metal precursors may be ionic or zwitterionic compounds, such as [M(CH₂Ph)₃ ⁺][B(C₆Fs)₄ ^"] or [M(CH₂Ph)₃ ⁺] [PhCH₂B(C₆Fs)₃-] where M is Zr or Hf. Activated metal precursors or such ionic compounds can be prepared in the manner shown, in Pellecchia et al., Organometallics 1994, 13, 298-302; Pellecchia et al., J. Am. Chem. Soc. 1993, 115, 1160-1162; Pellecchia et al., Organometallics 1993, 13, 3773-3775 and Bochmann et al., Organometallics 1993, 12, 633-640, each of which is incorporated herein by reference.

[058] The ligand to metal precursor compound ratio is typically in the range of about 0.01:1 to about 100:1, more specifically in the range of about 0.1:1 to about 10:1 and even more specifically about 1:1, 2: 1 or 3 : 1.

[059] As also noted above, in another aspect the invention relates to metal-ligand complexes. Generally, the ligand (or optionally a modified ligand as discussed above) is mixed with a suitable metal precursor (and optionally other components, such as activators) prior to or simultaneously with allowing the mixture to be contacted with the reactants (e.g., monomers). When the ligand is mixed with the metal precursor compound, a metal-ligand complex may be formed, which may itself be an active catalyst or may be transformed into a catalyst upon activation.

[060] Particular embodiments can include one or more of the following features. In particular embodiments, the complex can be characterized by the formula (II):

where B, X¹, X², X³, X⁴, X⁵, X⁶, X⁷, X⁸, R¹, R², R³, R⁴, R⁵, R⁶, and R⁷, are as described above for compounds of formulae (I) through formulae (Ic); M and L are as described above, m" is 0, 1, 2, 3, or 4 and the bonds between the heteroaromatic nitrogen (N) and the metal (M) is dative or absent, and may alternate between being present or absent. [061] The more specific embodiments for formula (Ia) through (Id) can bond in a similar format, giving embodiments including:

[062] As with the general formulas, the preferred X atoms, as shown in Tables 1 and 2 also apply to the metal complexes. More specific complexes include:

C

(HIc')

(HId')

(HIg')

[063] The metal-ligand complexes and compositions are active catalysts typically in combination with a suitable activator, combination of activators or activating technique, although some of the ligand-metal complexes may be active without an activator or activating technique depending on the ligand-metal complex and on the process being catalyzed. Broadly, the activator(s) may comprise alumoxanes, Lewis acids, Bronsted acids, compatible non-interfering activators and combinations of the foregoing. These types of activators have been taught for use with different compositions or metal complexes in the following references, which are hereby incorporated by reference in their entirety: U.S. Patents 5,599,761, 5,616,664, 5,453,410, 5,153,157, 5,064,802, EP-A-277,004 and Marks et ah, Chem. Rev. 2000, 100, 1391-1434. In some embodiments, ionic or ion forming activators are preferred. In other embodiments, alumoxane activators are preferred.

[064] Suitable ion forming compounds useful as an activator in one embodiment comprise a cation that is a Bronsted acid capable of donating a proton, and an inert, compatible, non-interfering, anion, A^". Suitable anions include, but are not limited to, those containing a single coordination complex comprising a charge-bearing metal or metalloid core. Mechanistically, the anion should be sufficiently labile to be displaced by olefmic, diolefmic and unsaturated compounds or other neutral Lewis bases such as ethers or nitriles. Suitable metals include, but are not limited to, aluminum, gold and platinum. Suitable metalloids include, but are not limited to, boron, phosphorus, and silicon. Compounds containing anions that comprise coordination complexes containing a single metal or metalloid atom are well known and many, particularly such compounds containing a single boron atom in the anion portion, are available commercially. [065] Specifically, such activators may be represented by the following general formula: (L*— H)_d ⁺(A^d-) wherein L* is a neutral Lewis base; (L* — H)⁺ is a Bronsted acid; A^d~ is a non-interfering, compatible anion having a charge of d-, and d is an integer from 1 to 3. More specifically A^d~ corresponds to the formula: (M^|3+ Q_h)^d~ wherein h is an integer from 4 to 6; h— 3 = d; M' is an element selected from group 13 of the periodic table; and Q is independently selected from the group consisting of hydrogen, dialkylamido, halogen, alkoxy, aryloxy, hydrocarbyl, and substituted-hydrocarbyl radicals (including halogen substituted hydrocarbyl, such as perhalogenated hydrocarbyl radicals), said Q having up to 20 carbons. In a more specific embodiment, d is one, i.e., the counter ion has a single negative charge and corresponds to the formula A^".

[066] Activators comprising boron or aluminum can be represented by the following general formula:

wherein: L* is as previously defined; M" is boron or aluminum; and Q is a fluorinated C i_₂o hydrocarbyl group. Most specifically, Q is independently selected from the group consisting of fluorinated aryl group, such as a pentafluorophenyl group {i.e., a CeFs group) or a 3,5-bis(CF3)2CeH₃ group. Illustrative, but not limiting, examples of boron compounds which may be used as an activating cocatalyst in the preparation of the improved catalysts of this invention are tri-substituted ammonium salts such as: trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate, tri(t- butyl)ammonium tetraphenylborate, N,N-dimethylanilinium tetraphenylborate, N₅N- diethylanilinium tetraphenylborate, N,N-dimethylanilinium tetra-(3,5- bis(trifluoromethyl)phenyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium) tetraphenylborate, trimethylammonium tetrakis(pentafluoroρhenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis(pentafluorophenyl) borate, tri(n-butyl)arnmonium tetrakis(pentafluorophenyl) borate, tri(secbutyl)arαrπoniiun tetraJkis(pentafluorophenyl) borate, N₅N- dimethylanilinium tetrakis(pentafluorophenyl) borate, N,N-diethylanilinium tetrakis(pentafluorophenyl) borate, N,N-diraethyl-(2,4,6-trimethylanilinitιin) tetrakis(pentafluorophenyl) borate, trimethylammonium tetrakis-(2,3,4,6- tetrafluorophenylborate and N,N-dimethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl) borate; dialkyl ammonium salts such as: di-(i-propyl)ammoniunα tetrakis(pentafluorophenyl) borate, and dicyclohexylammonium tetrakis(pentafluorophenyl) borate; and tri-substituted phosphonium salts such as: triphenylphosphonium tetrakis(pentatluoroplienyl) borate, tri(o-tolyl)phosρhonium tetrakis(pentafluorophenyl) borate, and tri(2,6-dimethylρhenyl)phosphonium tetrakisφentafluorophenyl) borate; N,N-dimethylanilmium tetrakis(3,5- bis(trifluoromethyl)phenyl)borate; HNMe(Ci₈H₃T)₂ ⁺B(C₆Fs)₄ ^"; HNPh(C_lsH3₇)2⁺B(C₆F₅)4^~ and ((4-nBu-Ph)NH(n-hexyl)₂)⁺B(C₆F₅)4^"" and ((4-nBu- Ph)NH(n-decyl)2)⁺B(C₆F₅)4^~ Specific (L*— H)⁺ cations are N,N-dialkylanilinium cations, such as HNMβ₂Ph⁺ ₃ substituted N,N-dialkylanilinium cations, such as (4-nBu- C₆H4)NH(n-C₆H₁₃)₂ ⁺ and (4-11Bu-C₆H₄)NH(U-C₁₀H₂O₂ ⁺ and HNMe(C _1SH₃₇)₂ ⁺. Specific examples of anions are tetrakis(3,5-bis(trifluoromethyl)phenyl)borate and tetrakis(pentafluorophenyl)borate. In some embodiments, the specific activator is PhNMe₂H⁺B(C₆Fs)₄-.

[067] Other suitable ion forming activators comprise a salt of a cationic oxidizing agent and a non-interfering, compatible anion represented by the formula: (Ox^e+)_d (A^d-)_e wherein: Ox⁶⁺ is a cationic oxidizing agent having a charge of e+; e is an integer from 1 to 3; and A^d~, and d are as previously defined. Examples of cationic oxidizing agents include: ferrocenium, hydrocarbyl-substituted ferrocenium, Ag⁺, or Pb⁺². Specific embodiments of A^d" are those anions previously defined with respect to the Bronsted acid containing activating cocatalysts, especially tetrakis(pentafluorophenyl)borate. [068] Another suitable ion forming, activating cocatalyst comprises a compound that is a salt of a carbenium ion or silyl cation and a non-interfering, compatible anion represented by the formula: ©⁺A^" wherein: ©⁺ is a C₁-_I0O carbenium ion or silyl cation; and A^" is as previously defined. A preferred carbenium ion is the trityl cation, i.e. triphenylcarbenium. The silyl cation may be characterized by the formula Z⁴Z⁵Z⁶Si⁺ cation, where each of Z⁴, Z⁵, and Z⁶ is independently selected from the group consisting of hydrogen, halogen, and optionally substituted alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, aryl, heteroaryl, alkoxyl, aryloxyl, silyl, boryl, phosphino, amino, mercapto, alkylthio, arylthio, and combinations thereof. In some embodiments, a specified activator is Ph₃C⁺B(C₆F₅)₄-

[069] Other suitable activating cocatalysts comprise a compound that is a salt, which is represented by the formula (A*^+a)_b(Z* J*_j)^~°d wherein A* is a cation of charge +a; Z* is an anion group of from 1 to 50, specifically 1 to 30 atoms, not counting hydrogen atoms, further containing two or more Lewis base sites; J* independently each occurrence is a Lewis acid coordinated to at least one Lewis base site of Z*, and optionally two or more such J* groups may be joined together in a moiety having multiple Lewis acidic functionality; j is a number from 2 to 12; and a, b, c, and d are integers from 1 to 3, with the proviso that a x b is equal to c x d. See WO 99/42467, which is incorporated herein by reference. In other embodiments, the anion portion of these activating cocatalysts may be characterized by the formula ((C₆F5)3M""-LN-M""(C₆F₅)3)^' where M"" is boron or aluminum and LN is a linking group, which is specifically selected from the group consisting of cyanide, azide, dicyanamide and imidazolide. The cation portion is specifically a quaternary amine. See, e.g., LaPointe, et al., J. Am. Chem. Soc. 2000, 122, 9560-9561 , which is incorporated herein by reference.

[070] In addition, suitable activators include Lewis acids, such as those selected from the group consisting of tris(aryl)boranes, tris(substituted aryl)boranes, tris(aryl)alanes, tris(substituted aryl)alanes, including activators such as tris(pentafluorophenyl)borane. Other useful ion forming Lewis acids include those having two or more Lewis acidic sites, such as those described in WO 99/06413 or Piers, et al., J. Am. Chem. Soc, 1999, 121, 3244-3245, both of which are incorporated herein by reference. Other useful Lewis acids will be evident to those of skill in the art. In general, the group of Lewis acid activators is within the group of ion forming activators (although exceptions to this general rule can be found) and the group tends to exclude the group 13 reagents listed below. Combinations of ion forming activators may be used.

[071] Other general activators or compounds useful in a polymerization reaction may be used. These compounds may be activators in some contexts, but may also serve other functions in the polymerization system, such as alkylating a metal center or scavenging impurities. These compounds are within the general definition of "activator," but are not considered herein to be ion-forming activators. These compounds include a group 13 reagent that may be characterized by the formula G¹³R⁵VpDp where G¹³ is selected from the group consisting of B, Al, Ga, In and combinations thereof, p is 0, 1 or 2, each R⁵⁰ is independently selected from the group consisting of hydrogen, halogen, and optionally substituted alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, aryl, heteroaryl, and combinations thereof, and each D is independently selected from the group consisting of halogen, hydrogen, alkoxy, aryloxy, amino, mercapto, alkylthio, arylthio, phosphino and combinations thereof. In other embodiments, the group 13 activator is an oligomeric or polymeric alumoxane compound, such as methylalumoxane and the known modifications thereof. See, for example, Barron, "Alkylalumoxanes, Synthesis, Structure and Reactivity", pp. 33-67 in Metallocene-Based Pofyolefins: Preparation, Properties and Technology, J. Schiers and W. Kaminsky (eds.), Wiley Series in Polymer Science, John Wiley & Sons Ltd., Chichester, England, 2000, and references cited therein. In other embodiments, a divalent metal reagent may be used that is defined by the general formula M'R⁵⁰2-_P'D_P' andp' is 0 or 1 in this embodiment and R⁵⁰ and D are as defined above. M' is the metal and is selected from the group consisting of Mg, Ca, Sr, Ba, Zn, Cd and combinations thereof. In still other embodiments, an alkali metal reagent may be used that is defined by the general formula M'^υR⁵⁰ and in this embodiment R⁵⁰ is as defined above. M^IV is the alkali metal and is selected from the group consisting of Li, Na, K, Rb, Cs and combinations thereof. Additionally, hydrogen and/or silanes may be used in the catalytic composition or added to the polymerization system. Silanes may be characterized by the formula SiR⁵V_qD_q where R⁵⁰ is defined as above, q is 1 , 2, 3 or 4 and D is as defined above, with the proviso that there is at least one D that is a hydrogen.

[072] The molar ratio of metal:activator (whether a composition or complex is employed as a catalyst) employed specifically ranges from 1: 10,000 to 100:1, more specifically from 1 :5000 to 10:1, most specifically from 1:10 to 1:1. ha one embodiment of the invention mixtures of the above compounds are used, particularly a combination of a group 13 reagent and an ion-forming activator. The molar ratio of group 13 reagent to ion- forming activator is specifically from 1:10,000 to 1000:1, more specifically from 1 : 5000 to 100: 1 , most specifically from 1 : 100 to 100: 1. In another embodiment, the ion forming activators are combined with a group 13 reagent. Another embodiment is a combination of the above compounds having about 1 equivalent of an optionally substituted N,N-dialkylaniliniurn tetrakis(pentafluorophenyl) borate, and 5-30 equivalents of a group 13 reagent. In some embodiments from about 30 to 2000 equivalents of an oligomeric or polymeric alurnoxane activator, such as a modified alumoxane (e.g., alkyialumoxane), can be used.

[073] In other applications, the ligand will be mixed with a suitable metal precursor compound prior to or simultaneous with allowing the mixture to be contacted to the reactants. When the ligand is mixed with the metal precursor compound, a metal-ligand complex may be formed, which may be a catalyst.

[074] The ligaπds, compositions, complexes and/or catalysts of the invention can be used to catalyze a variety of transformations, including, for example, oxidation, reduction, hydro genation, hydrosilylation, hydrocyanation, hydroformylation, polymerization, carbonylation, isomerization, metathesis, carbon-hydrogen activation, carbon-halogen activation, cross-coupling, Friedel-Crafts acylation and alkylation, hydration, Diels-Alder reactions, Baeyer-Villiger reactions, and other transformations. Some compositions, complexes and/or catalysts according to the invention are particularly effective at polymerizing ethylene or oc-olefϊns (such as propylene, 1-butene, l-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene and styrene), copolymerizing ethylene with α-olefins (such as propylene, 1-butene, l-pentene, 1-hexene, 1-heptene, 1-octene, and styrene), copolymerizing ethylene with 1,1-disubstituted olefins (such as isobutylene), or copolymerizing ethylene, propylene and a diene monomer suitable for production of EPDM (Ethylene-Propyl ene-Diene Monomer) synthetic rubbers. Thus, for example, in some embodiments, metal-ligand compositions and complexes containing zirconium or hafnium may be useful in the polymerization of propylene to form isotactic polypropylene or in the copolymerization of ethylene and one or more α-olefins, as noted above. In other embodiments, vanadium and chromium compositions and/or complexes according to the invention may be useful in, for example, the polymerization of ethylene. The compositions, complexes and/or catalysts according to the invention may also polymerize monomers that have polar functionalities in homopolymerizations or copolymer) zations and/or homopolymerize 1,1- and 1 ,2-disubstituted olefins. Also, diolefins in combination with ethylene and/or α-olefins or 1,1- and 1,2-disubstituted olefins may be copolymerized. hi some embodiments, catalysts incorporating the ligands, compositions and/or complexes of the present invention exhibit high catalytic activity in the polymerization of such α-olefins, including at high temperatures. [075] In general monomers useful herein may be olefinically unsaturated monomers having from 2 to 20 carbon atoms either alone or in combination. Generally, monomers may include olefins (including cyclic olefins), diolefins and unsaturated monomers including ethylene and C₃ to C₂0 α-olefms such as propylene, 1-butene, 1-hexene, 1- octene, 4-methyl-l-pentene, 1-norbornene, styrene and mixtures thereof; additionally, 1,1-disubstituted olefins, such as isobutylene, 2-methyl- 1-butene, 2-methyl-l-pentene, 2- ethyl- 1 -pentene, 2-methyl- 1 -hexene, 3 -trimethylsiZyl-2-methyl- 1 -propene,α-methyl- styrene, either alone or with other monomers such as ethylene or C3 to C₂o α-olefms and/or diolefms; additionally 1,2-substituted olefins, such as 2-butene. The α-olefins listed above may be polymerized in a stereospecific manner — for example, as in the generation of isotactic or syndiotactic or hemiisotactic polypropylene. Additionally the α-olefins may be polymerized to produce a polymer with differing tacticity sequences within the polymer chain, such as polypropylene containing atactic and isotactic sequences within the same polymer chain. Diolefins generally comprise 1,3-dienes such as (butadiene), substituted 1,3-dienes (such as isoprene) and other substituted 1,3-dienes, with the term substituted referring to the same types of substituents referred to above in the definition section. Diolefins also comprise 1,5-dienes and other non-conjugated dienes, such as ethylidene-norbornene, 1 ,4-hexadiene, dicyclopentadiene and other dienes used in the manufacture of EPDM synthetic rubbers. The styrene monomers may be unsubstituted or substituted at one or more positions on the aryl ring. The use of diolefins in this invention is typically in conjunction with another monomer that is not a diolefin. hi some embodiments, acetylenically unsaturated monomers may be employed. [076] The ligands, compositions, complexes, and/or catalysts of the invention may also be used to catalyze other (i.e., non-polymerization) transformations. For example, in some instances, substantially diastereomerically pure or substantially enantiomerically pure complexes may be useful for stereoselective, asymmetric, enantioselective, or diastereoselective reactions or transformations. Thus, in some embodiments substantially enantiomerically- or diastereomerically-pure complexes, ligand-metal compositions, and catalysts according to the invention may be used as asymmetric catalysts for a range of reactions, including polymerization reactions and other (non- polymerization) reactions, including many reactions useful in organic synthesis. In some embodiments, catalysts incorporating the compositions and complexes of the invention may be used to catalyze the asymmetric production of reaction products with enantiomeric excess (ee) or diastereomeric excess (de) of greater than 90% or greater than 99%. The asymmetric synthesis of chiral organic molecules is an important field, and is critical in the synthesis of many pharmaceuticals and other products. Single enantiomers of a chiral product can be prepared by a variety of techniques, including the resolution of racemates, or the use of substantially enantiomerically pure starting materials from the chiral pool of natural products, but for large scale synthesis the use of enantioselective catalysis is often the most attractive, and most economical, choice. See, e.g., Blaser et al., "Enantioselective Synthesis", pp. 1131-1149, in Applied Homogeneous Catalysis with Organometallic Compounds, Vol. 3, Cornils, B., & Herrmann, W. (eds.), 2nd Edition, Wiley- VCH, Weinheim, Germany, 2002, and Catalytic Asymmetric Synthesis, Ojima (ed.), VCH Publishers, Inc., New York, 1993, and the references cited therein.

[077] hi some embodiments, the complexes and catalysts of the invention may be chiral. Chiral group 4 metallocene complexes, especially chiral α/ωα-bridged metallocene complexes, have been used as asymmetric or enantioselective catalysts. See, e.g., Kuber, "Metallocenes as a Source of Fine Chemicals", pp. 893-902, in Applied Homogeneous Catalysis with Organometallic Compounds, VoI 2, Cornils, B., & Herrmann, W. (eds.), VCH, Weinheim, Germany, 1996, and Diamond et al., J. Am. Chem. Soc. 1996, 118, 8024-8033, and the references cited therein. Some of the disadvantages of group 4 metallocene based catalysts are described in WO 02/085820, including difficulty of synthesis and lack of thermal robustness. In common with the chiral group 4 metallocene systems described above, ligand-metal complexes, compositions, and catalysts of some embodiments of the invention possess Lewis-acidic metal centers in a chiral environment. However, in some embodiments the ligand-metal complexes, compositions, and catalysts of this invention show high thermal robustness and maintain high activity and high stereoselectivity at high temperatures, and may thus offer advantages over chiral Group 4 metallocenes for asymmetric or enantioselective catalysis.

[078] hi some embodiments, novel products, such as polymers, copolymers or interpolymers, may be formed having unique physical and/or melt flow properties. Such novel polymers can be employed alone or with other polymers in a blend to form products that may be molded, cast, extruded or spun. End uses for the polymers made with the catalysts of this invention include films for packaging, trash bags, bottles, containers, foams, coatings, insulating devices and household items. Also, such functionalized polymers are useful as solid supports for organometallic or chemical synthesis processes.

[079] The α-olefins listed above may be polymerized in a stereoselective manner to produce a substantially stereoregular polymer product (that is, a polymer product that is detectably enriched inm or r dyads (as determined, e.g., by ¹³C NMR) as compared to a corresponding atactic material), as in the generation of isotactic, syndiotactic or hemiisotactic poly-α-olefϊns. For example, in some embodiments 1-butene may be polymerized into isotactic poly- 1-butene. Additionally, the α-olefins may be polymerized to produce a polymer with differing tacticity sequences within the polymer chain, such as polypropylene containing atactic and isotactic sequences within the same polymer chain. The stereoregularity may be interrupted by stereoerrors, in particular isolated stereoerrors, which is an indication of enantiomorphic site control. Also, in some embodiments the isotactic polypropylene may include regioerrors as described in the literature (see, e.g., Resconi et al., Chem. Rev. 2000, 100, 1253-1345). [080] The ratio of 1-octene to ethylene incorporated in the ethylene-octene copolymer products was determined by FTIR. FTIR was performed on a Bruker Equinox 55 +IR Scope II in reflection mode using a Pike MappIR accessory with 16 scans. The ratio of 1- octene to ethylene incorporation was represented as the weight % (wt. %) of 1-octene incorporated in the polymer (wt. % 1-octene). Wt. % 1-octene was obtained from ratio of band heights at 1378 cm^"1 and 4335 cm^"1. This method was calibrated using a set of ethylene/ 1-octene copolymers with a range of known wt. % 1-octene content. [081] Polymerization is carried out under polymerization conditions, including temperatures of from -100⁰C to 300°C and pressures from atmospheric to 3000 atmospheres. Suspension, solution, slurry, gas phase or high-pressure polymerization processes may be employed with the catalysts and compounds of this invention. Such processes can be run in a batch, semi-batch or continuous mode. Examples of such processes are well known in the art. A support for the catalyst may be employed, which may be inorganic (such as alumina, magnesium chloride or silica) or organic (such as a polymer or cross-linked polymer). Methods for the preparation of supported catalysts are known in the art. Slurry, suspension, gas phase and high-pressure processes as known to those skilled in the art may also be used with supported catalysts of the invention.

[082] Other additives that are useful in a polymerization reaction may be employed, such as scavengers, promoters, modifiers and/or chain transfer agents, such as hydrogen, aluminum alkyls and/or silanes.

[083] As discussed herein, catalytic performance can be determined a number of different ways, as those of skill in the art will appreciate. Catalytic performance can be determined by the yield of polymer obtained per mole of metal complex, which in some contexts may be considered to be activity. The examples provide data for these comparisons.

[084] As stated herein, a solution process is specified for certain benefits, with the solution process being run at a temperature above 90⁰C, more specifically at a temperature above 100⁰C, further more specifically at a temperature above 110°C and even further more specifically at a temperature above 130⁰C. Suitable solvents for polymerization are non-coordinating, inert liquids. Examples include straight and branched-chain hydrocarbons such as isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, Isopar-E® and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; perhalogenated hydrocarbons such as perfluorinated C_4-Io alkanes, chlorobenzene, and aromatic and alkyl substituted aromatic compounds such as benzene, toluene, mesitylene, and xylene. Suitable solvents also include liquid olefins which may act as monomers oτ comonomers including ethylene, propylene, 1 -butene, butadiene, cyclopentene, 1-hexene, 1-pentene, 3 -methyl- 1-pentene, 4-methyl-l-pentene, 1,4-hexadiene, 1-octene, 1-decene, isobutylene, styrene, divinylbenzene, allylbenzene, and vinyltoluene (including all isomers alone or in admixture). Mixtures of the foregoing are also suitable.

[085] The ligands, metal-ligand complexes and compositions of this invention can be prepared and tested for catalytic activity in one or more of the above reactions in a combinatorial fashion. Combinatorial chemistry generally involves the parallel or rapid serial synthesis and/or screening or characterization of compounds and compositions of matter. U.S. Patent Nos. 5,985,356, 6,030,917 and WO 98/03521, all of which are incorporated herein by reference, generally disclose combinatorial methods. In this regard, the ligands, metal-ligand complexes or compositions may be prepared and/or tested in rapid serial and/or parallel fashion, e.g., in an array format. When prepared in an array format, ligands, melal-ligand complexes or compositions may take the form of an array comprising a plurality of compounds wherein each compound can be characterized by any of the above general formulas (i.e., I, II, III, etc.). An array of ligands may be synthesized using the procedures outlined previously. The array may also be of metal precursor compounds, the metal-ligand complexes or compositions characterized by the previously described formulae and/or description. Typically, each member of the array will have differences so that, for example, a ligand or activator or metal precursor or R group in a first region of the array may be different than the ligand or activator or metal precursor or R group in a second region of the array. Other variables may also differ from region to region in the array.

[086] In such a combinatorial array, typically each of the plurality of compositions or complexes has a different composition or stoichiometry, and typically each composition or complex is at a selected region on a substrate such that each compound is isolated from the other compositions or complexes. This isolation can take many forms, typically depending on the substrate used. If a flat substrate is used, there may simply be sufficient space between regions so that there cannot be interdiffusion between compositions or complexes. As another example, the substrate can be a microtiter or similar plate having wells so that each composition or complex is in a region separated from other compounds in other regions by a physical barrier. The array may also comprise a parallel reactor or testing chamber.

[087] The array typically comprises at least 8 compounds, complexes or compositions each having a different chemical formula, meaning that there must be at least one different atom or bond differentiating the members in the array or different ratios of the components referred to herein (with components referring to ligands, metal precursors, activators, group 13 reagents, solvents, monomers, supports, etc.). In other embodiments, there are at least 20 compounds, complexes or compositions on or in the substrate each having a different chemical formula. In still other embodiments, there are at least 40 or 90 or 124 compounds, complexes or compositions on or in the substrate each having a different chemical formula. Because of the manner of forming combinatorial arrays, it may be that each compound, complex or composition may not be worked-up, purified or isolated, and for example, may contain reaction by-products or impurities or unreacted starting materials. [088] The catalytic performance of the compounds, complexes or compositions of this invention can be tested in a combinatorial or high throughput fashion. Polymerizations can also be performed in a combinatorial fashion, see, e.g., U.S. Patent Nos. 6,306,658, 6,508,984 and WO 01/98371, each of which is herein incorporated by reference.

EXAMPLES

[089] General: All air sensitive reactions were performed under a purified argon or nitrogen atmosphere in a Vacuum Atmospheres or MBraun glove box. AU solvents used were anhydrous, de-oxygenated and purified according to known techniques. All ligands and metal precursors were prepared according to procedures known to those of skill in the art, e.g., under inert atmosphere conditions, etc. Ethylene/1-octene copolymerizations were carried out in a parallel pressure reactor, which is described in U.S. Patents 6,306,658, 6,455,316, 6,489,168, 6,759,014, 6,913,934 and WO 00/09255, each of which is incorporated herein by reference.

[090] High temperature Size Exclusion Chromatography was performed using an automated "Rapid GPC" system as described in U.S. Patents 6,491,816, 6,491,823, 6,475,391, 6,461,515, 6,436,292, 6,406,632, 6,175,409, 6,454,947, 6,260,407, and 6,294,388 each of which is incorporated herein by reference. In the current apparatus, a series of two 30 cm x 7.5 mm linear columns is used, with both columns containing PLgel lOum, MixB (available from Polymer Labs). The GPC system was calibrated using narrow polystyrene standards. Unless otherwise indicated, the system was operated at an eluent flow rate of 1.5 mL/min and an oven temperature of 160⁰C; o- dichlorobenzene was used as the eluent; the polymer samples were dissolved 1,2,4- trichlorobenzene at a concentration of about 5 mg/mL; 200 μL of a polymer solution were injected into the system; and the concentration of the polymer in the eluent was monitored using an evaporative light scattering detector. All of the molecular weight results obtained are relative to linear polystyrene standards.

[091] FTIR spectra are obtained using thin films deposited from solution onto gold coated Si wafers acquired at 4 cm^"1 resolution and with 16 scans in reflection-absorption mode on a Bruker Equinox 55 FTIR spectrometer equipped with a Pike MappIR accessory with 16 scans. The ratio of 1-octene to ethylene incorporation was represented as the weight % (wt. %) of 1-octene incorporated in the polymer (wt. % 1-octene). Wt. % 1-octene was obtained from ratio of band heights at 1378 cm^"1 and 4335 cm^'1. This method was calibrated using a set of ethylene/1 -octene copolymers with a range of known wt. % 1 -octene content. Mol% 1-octene incorporation was calculated from the obtained wt. % 1-octene content.

[092] I. Ligand Synthesis

[093] Ligands Al, A2, A4, and A5 were synthesized in a manor similar to Ligand A3 (Example 1), making the appropriate changes in alkyl diiodide starting material for the desired ligand structure. Ligands Bl, B2, B4, and B5 were synthesized in a manor similar to Ligand B3 (Example 2), making the appropriate changes in the dicarboxylic acid starting material for the desired ligand structure. Building block AA(4) was custom synthesized in two steps (bromination, cyanation) from commercial A-tert- butylphenylphenol (Avocado Research Chemicals, Ltd) by Syngene (Bangalore, India) using standard procedures known to those skilled in the art (see Weissman, S. A.; Zewge, D.; Chen, C. J. Org. Chem. 2005, 70, 1508). iV-chlorosuccinimide is abbreviated as NCS.

[094] Example 1: Synthesis of Ligand A3

A3

[095] Step 1: Synthesis of Diacetal AA(I)

AA(1)

[096] Step 2: Synthesis of DiaJdehyde AA(2)

AA(1) AA(2)

[097] Step 3: Synthesis of Dioxime AA(3)

AA(2) AA(3)

[0Θ8] Step 4: Synthesis of Ligand A3

[099] Experimental Details

[010O] 2-(l,3-Dioxan-2-yl)phenylmagnesitun bromide (0.25 M in THF, 16.0 niL, 4.00 mmol, 4.00 eq), 1,5-diiodopentane (0.324 g, 1.00 mmol, 1.00 eq), and copper(I) iodide were combined and heated at 40 ⁰C for 18h. The reaction was cooled to room temperature and volatiles removed under N₂ purge. The residue was taken up in diethyl ether and washed once with H₂O. The ether layer was dried over Na₂SO₄, filtered, and concentrated. The crude material was purified by flash chromatography (0-20% EtOAc/hexane) Io yield 0.23 g (57%) of the desired product AA(I) as a clear oil. ¹U NMR (CD₂Cl₂, 300 MHz): 7.55 (d, J - 7.8 Hz, 2H), 7.31-7.16 (m, 6H), 5.63 (s, 2H)₅ 4.22 (dd, J = 10.5 Hz, J = 5.1 Hz, 4H), 3.97 (dt, J= 12.3 Hz, J= 2.4 Hz, 4H), 2.72 (t, J= 7.5 Hz, 4H), 230-2.10 (m, 2H), 1.64 (m, 4H), 1.52-1.40 (m, 4H). [0101] The diacetal AA(I) (0.225 g, 0.567 mmol) was taken up in THF (3 mL) and 6 M HCl (0.50 mL) added. The reaction was heated at 50 ⁰C for 4 h. The solution was cooled to room temperature, diluted with H₂O, and extracted with Et₂O. The Et₂O layer was separated and dried over Na₂SO₄. After filtering, the crude material was concentrated and purified by flash chromatography (0-15% EtOAc/hexane) to yield 0.116 g (73%) of the desired product AA(2). ¹H NMR (CD₂Cl₂, 300 MHz): 10.28 (s, 2H), 7.82 (d, J= 7.5 Hz, 2H), 7.52 (t, J= 7.5 Hz, 2H), 7.38 (t, J= 7.5 Hz, 2H), 7.29 (d, J= 1.5 Hz₅ 2H), 3.04 (t, J= 6.0 Hz₅4H), 1.80-1.40 (m, 8H).

[0102] The dialdehyde AA(2) (0.12 g, 0.41 mmol, 1.00 eq) was taken up in EtOH (2.0 mL). Hydroxylamine hydrochloride (69 mg, 0.99 mmol, 2.4 eq) and pyridine (79 mg, 0.99 mmol, 2.4 eq) were added to the solution. The reaction was heated at 80 ⁰C for 3 h and then cooled to room temperature. Volatiles were removed under N₂ purge and the residue redissolved in EtOAc. The organics were washed once with H₂O, separated, and dried over Na₂SO₄. After filtering, the material was concentrated to yield 0.13 g (98%) of the desired product AA(3). ¹H NMR (CD₂Cl₂, 300 MHz): 8.43 (s, 2H), 7.69 (d, J= 7.5 Hz, 2H), 7.32 (dt, J= 7.5 Hz, J = 1.2 Hz, 2H), 7.22 (t, J= 6.6 Hz, 4H), 2.75 (t, J= 7.5 Hz, 4H), 1.61 (m, 4H), 1.46 (m, 2H).

[0103] The dioxime AA(3) (0.126 g, 0.406 mmol, 1.00 eq) was taken up in anhydrous CHCl₃ (1.00 mL) under an atmosphere of Ar. N-chlorosuccinimide (0.163 g, 1.22 mmol, 3.00 eq) was added in a single portion followed by addition of pyridine (81 μmol, 10 μL, 0.20 eq). The sides of the reaction flask were rinsed with additional CHCI3 (1.00 mL) and the reaction stirred at room temperature for 2 h. Volatiles were removed under N₂ purge. Anhydrous cyclohexane was added and volatiles again removed. The resulting light yellow solid was then suspended in anhydrous cyclohexane (2.00 mL) and the phenol nitrile AA(4) (0.408 g, 1.62 mmol, 4.00 eq) added. 2,6-lutidine (0.893 mmol, 100 μL, 2.20 eq) was added, the reaction vessel sealed and the mixture heated at 80 ⁰C for 18 h. The reaction was cooled to room temperature and volatiles removed under N₂ purge. The crude material was purified by flash chromatography (0-15% EtOAc/hexane) to yield 37 mg (11%) of the desired product A3. ¹H NMR (CD₂Cl₂, 300 MHz): 10.77 (s, 2H)₅ 8.03 (s, 2H), 7.93 (d, J= 7.8 Hz, 2H), 7.68-7.58 (m, 6H)₅ 7.50-7.30 (m, 6H), 3.02 (t, J= 7.5 Hz₅ 4H)₅ 1.68 (m, 4H), 1.50 (m, 2H)₅ 1.40 (S₅ 18H).

[0104] Example 2: Synthesis of luigand B3

B3

[0105] Step 1: Synthesis of Methyl Protected Phenol Nitrile

AA(4) BB(1)

[0106] Step 2: Synthesis of Amide Oxime

BB(1) BB(2)

[0107] Step 3: Synthesis of Methyl Protected Ligand B3

BB(2) BB(3)

[0108] Step 4: Synthesis of Ligand B3

[0109] Experimental Details

[0110] Phenol AA(4) (1.00 g, 3.98 πunol, 1.00 eq) was taken up in anhydrous acetone (20 mL). K₂CO₃ (1.10 g, 7.96 mmol, 2.00 eq) and dimethylsulfate (0.653 g, 0.49 mL, 5.17 mmol, 1.30 eq) were added and the reaction heated at 60 ⁰C for 4 h. The crude material was concentrated and purified by flash chromatography (0-15% EtOAc/hexane) to yield 0.83 g (78%) of the desired product BB(I). ¹H NMR (CD₂Cl₂, 300 MHz): 7.59 (s, 2H), 7.58-7.39 (m, 5H), 3.62 (s, 3H), 1.34 (s, 9H). [0111] The phenol nitrile BB(I) (1.01 mmol, 1.00 eq) was taken up in EtOH (5.00 mL). Hydroxyl amine (50 wgt% in H₂O, 0.270 g, 4.03 mmol, 4.00 eq) was added, the reaction sealed, and the mixture heated at 80 ⁰C for 18 hr. EtOAc and sat'd aq. NaCl were added to the cooled reaction mixture and the organic layer separated and dried over Na₂SO₄. After filtration and solvent removal, the desired product BB(2) was obtained in 98% yield. ¹H NMR (CD₂Cl₂, 300 MHz): 7.64 (d, J - 3.0 Hz, IH), 7.57 (m, IH)₅ 7.55 (m, IH), 7.49-7.34 (m, 4H), 5.48 (bs, 2H), 3.44 (s, 3H), 1.37 (s, 9H). [0112] Amide oxime BB(2) (0.200 g, 0.670 mmol, 2.20 eq), glutaric acid (0.049 g, 0.305 mrnol, 1.00 eq), l-(3-Dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (0.128 g, 0.670 mmol, 2.20 eq), and 4-dimethylaminopyridine (0.082 g, 0.670 mmol, 2.20 eq) were combined in dry dioxane (6.00 mL). The mixture was heated at 100 ⁰C for 18 h. The reaction was cooled to room temperature and volatiles removed under N₂ purge. The residue was suspended in CH₂Cl₂ and washed with H₂O. The organics were dried over Na₂SO₄, filtered, and concentrated. The crude material was purified by flash chromatography (0-15% EtOAc/hexane) to yield 0.15 g (72%) of the desired product BB(3) as a white solid. ¹H NMR (CD₂Cl₂, 300 MHz): 9.74 (s, 2H), 8.03 (d, J - 2.7 Hz, 2H), 7.63-7.30 (rα, 12H), 3.05 (t, J = 7.5 Hz, 4H), 2.00 (m, 4H), 1.62 (m, 2H), 1.37 (s, 18H).

[0113] The bridged oxadiazole BB(3) (0.151 g, 0.220 mmol, 1.00 eq) was taken up in dry CH₂Cl₂ (4.50 mL) and cooled to -78 ⁰C in a dry ice/acetone bath. The cooled solution was treated with BBr₃ (1.0 M in CH₂Cl₂, 0.55 mL, 0.55 mmol, 2.5 eq) and the reaction allowed to slowly warm to room temperature and stir for 4 h. The reaction was then recooled to -78 ⁰C and quenched by dropwise addition of MeOH. The solution was then passed through a short plug of silica and concentrated to a light orange oil. The crude material was purified by flash chromatography (0-20% EtOAc/hexane) to yield 0.117 g (81%) of the desired product B3. ¹H NMR (CD₂Cl₂, 300 MHz): 9.74 (s, 2H), 8.03 (d, J= 2.7 Hz, 2H)₃ 7.63-7.30 (m, 12H), 3.05 (t, J= 7.5 Hz, 4H), 2.00 (m, 4H), 1.62 (m, 2H), 1.37 (s, 18H).

[0114] Example 3: Synthesis of Ligand Cl

C1

[0115] Step 1: Synthesis of Diiodide

CC{1)

[0116] Step 2: Synthesis of MOM Protected Phenol

CC(2)

[0117] Step 3: Synthesis of Phenol Thiazole Building Block

CC(2) CC(3)

[0118] Step 4: Synthesis of MOM Protected Bridged Phenol Thiazole

CC(4)

[0119] Step 5: Synthesis of Ligand Cl

CC(4) C1 [0120] Experimental Details

[0121] NaH (95%, 3.36 g, 133 πxmol, 3.00 eq) was placed in a round bottom flask and anhydrous DMF (88 mL) added. The suspension was cooled to 0 ⁰C and 4-tert- butylphenylphenol (10.0 g, 44.2 mmol, 1.00 eq) added in portions. Once evolution OfH₂ (g) has ceased (~ 30 min), chloromethyl methyl ether (10.7 g, 10.1 mL, 133 mmol, 3.00 eq) was added dropwise. The reaction was allowed to warm to room temperature and stir for several hours. The reaction was then cooled to 0 ⁰C and quenched by dropwise addition of H₂O. The solution was extracted with EtOAc, the organics dried over Na₂SO₄, filtered, and concentrated. DMF was removed by passing the crude material through a plug of silica with 100% hexane. The hexane solution was concentrated to give 11.8 g (99%) of the desired product CC(2) as a viscous clear oil. ¹H NMR (CD₂Cl₂, 300 MHz): 7.51 (d, J= 8.4 Hz₅ 2H), 7.41 (t, J= 7.5 Hz, 2H), 7.36-7.28 (m, 3H)₅ 7.13 (d, J= 9.0 Hz, IH), 5.09 (s, 2H), 3.36 (s, 3H), 1.33 (s, 9H). .

[0122] MOM protected phenylphenol CC(2) (0.500 g, 1.85 mmol, 1.10 eq) was taken up in anhydrous Et₂O (2.00 mL) and "BuLi (1.6 M in hexane, 1.4 mL, 1.9 mmol, 1.0 eq) added dropwise. The solution was allowed to stir for 18 h at room temperature. Trimethyl borate (0.21 g, 0.23 mL, 2.0 mmol, 1.1 eq) was added dropwise and the reaction allowed to stir for 1 h. H₂O (1.00 mL) was then added and stirring continued for an additional 1 h. Volatiles were then removed under N₂ purge and the remaining material diluted with ethylene glycol dimethyl ether (9 mL). Na₂CO₃ (0.356 g, 3.36 mmol, 2.00 eq) and 2,4-dibromothiazole (0.408 g, 1.68 mmol, 1.00 eq) were added. The solution was deoxygenated with Ar for 30 min and then Pd(PPh₃)₄ (0.196 g, 0.170 mmol, 10 mole %) added. The reaction vessel was sealed and the mixture heated at 80 ⁰C for 18 h. The reaction was cooled to room temperature and volatiles removed under N₂ purge. The residue was diluted with CH₂Cl₂, washed with H₂O, dried over Na₂Sθ₄, filtered, and concentrated. The crude material was purified by flash chromatography to yield 0.650 g (89%) of the desired product CC(3) as a viscous oil. ¹H NMR (CD₂Cl₂, 300 MHz): 8.24 (s, IH), 7.57 (d, J- 8.1 Hz, 2H), 7.50-7.33 (m, 5H), 4.60 (s, 2H), 3.02 (s, 3H), 1.38 (s, 9H).

[0123] Aryl diiodide CC(I) (0.150 g, 0.346 mmol, 1.00 eq) was taken up in anhydrous Et₂O (4.00 mL) and cooled to -20 ⁰C. Cold "BuLi (1.6 M, 0.45 mL, 0.73 mmol, 2.1 eq) was added dropwise and the reaction maintained at -20 ⁰C for 1 h, during which time a white precipitate formed. ZnCl₂ (0.50 M in THF, 1.45 mL, 0.726 mmol, 2.10 eq) was added and the solution stirred at room temperatue for 30 minutes. Volatiles were removed under N₂ purge and the residue redissolved in THF (2.50 mL). Pd₂(dba)3 (4.0 mg, 4,0 μmoL 1.0 mole %), 2-dicyclohexylρhospMno-2\6'-diisopropoxy-l,l'-biphenyl (Ruphos, Strem) (7.0 mg, 14 μmol, 4 mole %), and the thiazole bromide CC(3) (0.329 g, 0.761 mmol, 2.20 eq) were added. The reaction vessel was sealed under N₂ and heated to 70 °C for 18 h. The solution was cooled to room temperature and volatiles removed under N₂ purge. The crude material was purified by flash chromatography (8-15% Et₂O/hexane) to yield 38 mg (13%) the desired product CC(4). ¹H NMR (CD₂Cl₂, 300 MHz): 8.34 (s, 2H), 7.61 (d, J = 6.9 Hz, 4H), 7.50-7.10 (m, 18H), 4.63 (s, 4H), 3.21 (s, 4H)₅ 2.99 (s, 6H), 1.32 (s, 18H).

[0124] MOM protected phenol thiazole CC(4) (38 mg, 43 μmol) was taken up in THF (1.0 mL) and MeOH (0.50 mL) added to the solution. Concentrated HCl (0.25 mL) was added to the solution and the reaction allowed to stir at 40⁰C until the reaction had gone to completion as indicated by TLC analysis. Volatiles were removed under N₂ purge and the residue brought to pH 7 with aq. NaHCθ₃. The solution was extracted with CH₂CI₂ and the organics dried over Na₂SO₄. The solution was filtered, concentrated, and purified by flash chromatography (0-5% Et₂O/hexane) to yield 4 mg (12%) of the desired product Cl. ³H NMR (CD₂Cl₂, 300 MHz): 12.47 (s, 2H), 7.64 (d, J- 2.4 Hz, 2H), 7.62- 7.57 (m, 4H), 7.46-7.12 (m, 16H), 6.97 (s, 2H), 3.05 (s, 4H), 1.39 (s, 18H).

[0125] II. Polymerization Reactions

[0126] Example 4: Ethylene-1-Octene copolymerizations using metal-ligand compositions

[0127] A total of 13 separate ethylene- 1-octene polymerization reactions (EO1-EO13) were performed as follows. (Table 3)

[0128] Preparation of the polymerization reactor prior to injection of catalyst composition: A pre- weighed glass vial insert and disposable stirring paddle were fitted to each reaction vessel of the reactor. The reactor was then closed, 0.200 mL of a 0.05 M solution of nonhydrolytic polymethylaluminoxane (Akzo Nobel PMAO-IP, referred to below as "PMAO", available from Akzo Nobel Polymer Chemicals, Chicago, Illinois, USA) in toluene, 0.330 mL of octene and 3.2 mL of toluene were injected into each pressure reaction vessel through a valve. The temperature was then set to the appropriate setting (with specific temperatures for each polymerization being listed in Table 3, below), and the stirring speed was set to 800 rpm unless otherwise noted. The mixture was exposed to ethylene at 100 psi pressure. An ethylene pressure of 100 psi in the pressure cell and the temperature setting were maintained, using computer control, until the end of the polymerization experiment.

[0129] In situ preparation of metal-ligand compositions: The following method was employed to prepare the metal-ligand compositions as indicated in Table 3: 50 μL of the ligand solution (10 mM in toluene) was dispensed in a ImL glass vial. To the 1 mL glass vial containing the ligand was added an equimolar amount of the metal precursor solution (10 mM in toluene) to form the metal-ligand composition solution followed by the addition of 50-100 μL toluene. The reaction mixture was kept at ambient temperature prior to screening.

[0130] Preparation of the group 13 reagent and activator stock solutions: The

"activator solution" is either a solution of [HN(CioH2i)₂(-p«ra-C4H₉-Ph)]⁺[B(C6F₅)4]^" ₅ (SJ2BF20) in toluene or a solution of PMAO in toluene. The identity and molarity of this solution is indicated in the "activation method" of the individual example described below. The "group 13 reagent" solution is either a solution of triisobutylaluminium ("TIBA") in toluene or a solution of PMAO in toluene. The identity and molarity of this solution is indicated in the "activation method" of the individual example described below.

[0131] Activation methods and injection of solutions into the pressure reactor vessel: The following methods were employed to activate and inject the metal-ligand compositions for the examples in Table 3: Method AAAA: To the 1 mL glass vial containing the metal-ligand composition, the appropriate amount of the group 13 reagent solution as a 50 mM solution, containing the indicated equivalents (per metal precursor) in the specific example, was added. After about 1 minute, the appropriate amount of the activator solution (2.5 mM in toluene), containing the indicated equivalents (per metal precursor), was added to the 1 mL vial and the reaction mixture was mixed. Approximately 90 seconds later, a fraction of the 1 mL vial contents corresponding to the indicated "catalyst amount injected", based on micromoles (μmol) of metal precursor, was injected into the pre-pressurized reaction vessel and was followed immediately by injection of toluene to bring the total volume injected to 0.7 mL. Method BBBB: To the 1 mL glass vial containing the metal-ligand composition, the appropriate amount of the group 13 reagent solution as a 50 mM solution, containing the indicated equivalents (per metal precursor) in the specific example, was added. After about 1 minute, the appropriate amount of the activator solution (2.5 mM), containing the indicated equivalents (per metal precursor), was added to the 1 mL vial followed by an immediate addition of 600 μL of toluene. The contents of the 1 mL vial were mixed. Approximately 1 minute later, a fraction of the 1 mL vial contents corresponding to the indicated "catalyst amount injected", based on micromoles (μmol) of metal precursor, was injected into the pre-pressurized reaction vessel and was followed immediately by injection of toluene to bring the total volume injected to 0.7 mL. Method CCCC: Similar to Method AAAA except the molarity of the activator and group 13 reagent solutions was 600 mM. Method DDDD: Similar to Method BBBB except the molarity of the activator and group 13 reagent solutions was 600 mM.

[0132] Polymerization: The polymerization reaction was allowed to continue for 112- 1800 seconds, during which time the temperature and pressure were maintained at their pre-set levels by computer control. The specific times for each polymerization are shown in Table 3. The polymerization times were the lesser of the maximum desired polymerization time or the time taken for a predetermined amount of monomer gas to be consumed in the polymerization reaction. After the reaction time elapsed, the reaction was quenched by addition of an overpressure of carbon dioxide sent to the reactor.

[0133] Product work up: ethylene/1-octene copolymerizations: After the polymerization reaction, the glass vial insert, containing the polymer product and solvent, was removed from the pressure cell and removed from the inert atmosphere dry box. The volatile components were removed using a centrifuge vacuum evaporator. After substantial evaporation of the volatile components, the vial contents were dried thoroughly by evaporation at elevated temperature under reduced pressure. The vial was then weighed to determine the yield of polymer product. The polymer product was then analyzed by rapid GPC, as described above to deteπnine the molecular weight of the polymer produced, and FTIR spectroscopy to determine the comonomer incorporation. Results are presented in Table 3.

Table 3: Select Examples of Ethylene-1-Octene Copolymerization with in situ prepared Metal-Ligand Compositions

4- -4

[0134] Preferred embodiments of the invention include:

[0135] Embodiment 1: A metal ligand complex characterized by the formula:

wherein X¹ is N or C, X² is O, S, N(R⁵V or CR⁵, X³ is O, S, N(R⁶)_n» or CR⁶, X⁴ is O, S, N(R⁷V- or CR⁷, wherein each n', n", and n'" are each independently 0 or 1, provided that the heteroatom containing ring system is heteroaromatic,

X⁵ is N or C, X⁶ is O, S₅ N(R⁵V or CR⁵, X⁷ is O, S, N(R⁶V- or CR⁶, X⁸ is

0, S, N(R⁷V_'" or CR⁷, wherein eachn', n", and n'" are each independently O or

1, provided that the heteroatom containing ring system is heteroaromatic;

B is a bridging group linking the heteroaromatic rings and having up to 50 atoms in the bridge not counting hydrogen atoms, provided that the bridging group links one of X², X³, or X⁴ to one of X⁶, X⁷, or X⁸; each R¹, R², R³, R⁴, R⁵, R⁶, and R⁷ are the same or different from each other and are independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, halo, silyl, boryl, phosphino, amino, thioalkyl, thioaryl, and combinations thereof, optionally two or more of R¹, R², R³, and R⁴ on any one ring may be joined to form a fused ring system having up to 50 atoms, not counting hydrogen atoms; and optionally two or more of R⁵, R⁶, and R⁷ on any one ring may be joined to form a fused ring system having up to 50 atoms, not counting hydrogen atoms; M is a metal selected from the group consisting of groups 3 through 6 of the Periodic Table of Elements and lanthanides; each L is independently selected from the group consisting of hydrogen, halogen, optionally substituted alkyl, heteroalkyl, allyl, diene, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, aryl, hetcroaryl, alkoxy, aryloxy, boryl, silyl, amino, phosphino, ether, thioether, phosphine, amine, carboxylate, alkylthio₅ arylthio, 1,3-dionate, oxalate, carbonate, nitrate, sulphate, and combinations thereof; and m" is θ, 1, 2, 3, or 4.

[0136] Embodiment 2: The metal ligand complex of embodiment 1, wherein the complex is characterized by the general formula:

or the general formula

[0137] Embodiment 3: The metal ligand complex of embodiment 2, wherein the complex is characterized by the general formula:

or the general formula

[0138] Embodiment 4: The compound of embodiment 3, wherein the metal ligand complex is characterized by the formula

or the formula

or the formula

or the formula

or the formula

or the formula

or the formula

or the formula

or the formula

or the formula

[0139] Embodiment 5: The compound of embodiment 3, wherein the metal ligand complex is characterized by the formula

(C) or the formula

(d') or the formula

or the formula

[0140] Embodiment 6: The complex of any of the above embodiments, wherein

B is selected from the group consisting of divalent, optionally substituted alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, aryl, heteroaryl and silyl.

[0141] Embodiment 7: The complex of any of the above embodiments, wherein the bridging group B is substituted with one or more optionally substituted hydrocarbyl or heteroatom-containing hydrocarbyl groups. [0142] Embodiment 8: The complex of any of the above embodiments, wherein B is represented by the general formula -(Q"R⁴⁰2-z")z' ~ wherein each Q" is independently either carbon or silicon and wherein each R⁴⁰ substituent is independently selected from the group consisting of hydrogen and optionally substituted hydrocarbyl and heteroatom containing hydrocarbyl, wherein two or more R⁴⁰ substituents are optionally joined into a ring structure having from 3 to 50 atoms in the ring structure not counting hydrogen atoms; z' is an integer from 1 to 20; and z" is 0, 1 or 2.

[0143] Embodiment 9: The complex of any of the above embodiments, wherein - B- is selected from the group consisting of

wherein each Q is independently selected from the group consisting of carbon and silicon, each R⁶⁰ is independently selected from the group consisting of hydrogen and optionally substituted hydrocarbyl and heteroatom containing hydrocarbyl, provided that at least one R⁶⁰ substituent is not hydrogen, wherein the R⁶⁰ substituents are optionally joined into a ring structure having from 3 to 50 atoms in the ring structure not counting hydrogen atoms, and m' is 0, 1, or 2. [0144] Embodiment 10: The complex of any of the above embodiments, wherein -B- is selected from the group consisting Of-(CH₂)-, -(CH₂^-, -(CH₂)3-,-(CH₂)4-, -(CH₂)S-, -(CH₂)₆-,-(CH₂)₇-, -(CH₂)S-, -(CH(CH₃))-, ~(CH(CH₃))₂-, -(C(CHj)₂)-, -(C(CH₃)2)₂-, -(C(CH₃)₂)₃-, -CH₂CH(CH₃)CH₂-, -CH₂C(CH₃)₂CH₂- -CH₂CH(C₆H₅)CH₂-, -CH(CH₃)CH₂CH(CH₃)-, -CH(C₂H₅)CH₂CH(C₂H₅)-, -CH(CH₃)CH₂CH₂CH(CH₃)-, -CH(C₆H₅)CH₂CH(C₆H₅)- -CH(C₆H₅)CH₂CH(C₆H₃H -(C₆H₄)CH₂CH₂(C₆H₄K -(C₆H₄)CH₂CH₂CH₂(C₆H₄)' -(C₆H₄)CH₂CH₂CH₂CH₂(C₆H₄)-,

[0145] Embodiment 11 : The complex of any of the above embodiments, wherein -B- is represented by the formula

where (Q"R⁴⁰2-z")_z' is defined in claim 8 and wherein each R⁸⁰ substituent is independently selected from the group consisting hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, halo, silyl, boryl, phosphino, amino, thioalkyl, thioaryl, and combinations thereof, optionally two or more of R⁸⁰ groups on any one ring may be joined to form a fused ring system having up to 50 atoms, not counting hydrogen atoms.

[0146] Embodiment 12: The complex, of any of the above embodiments, wherein the complex is asymmetric across the bridging group.

[0147] Embodiment 13: The complex of any of the above embodiments, wherein the complex is asymmetrical in the selection of the C, N, O or S atoms in the heterocycle rings such that, at least, either X¹ and X⁵ are different or X² and X⁶ are different or X³ and X⁷ are different or X⁴ and X⁸ are different. [0148] Embodiment 14: The complex of any of the above embodiments, wherein the complex is symmetric across the bridging group B. [0149] Embodiment 15: The complex of any of the above embodiments, wherein R¹ is not hydrogen.

[0150] Embodiment 16: The complex of any of the above embodiments, wherein R¹ is selected from the group consisting of optionally substituted alkyl, heteroalkyl, aryl and optionally substituted aryl. [0151] Embodiment 17: A compound characterized the formula:

wherein X¹ is N or C, X² is O, S, N(R⁵V or CR⁵, X³ is O, S, N(R⁶V' or CR⁶, X⁴ is O, S, N(R⁷V- or CR⁷, wherein eachn', n", and n'" are each independently 0 or 1, provided that the heteroatom containing ring system is heteroaromatic,

X⁵ is N or C, X⁶ is O₅ S, N(R⁵V or CR⁵, X⁷ is O, S, N(R⁶)_n» or CR⁶, X⁸ is

0, S, N(R⁷V- or CR⁷, wherein each n\ n", andn'" are each independently 0 or

1 , provided that the heteroatom containing ring system, is heteroaromatic;

B is a bridging group linking the heteroaromatic rings and having up to 50 atoms in the bridge not counting hydrogen atoms, provided that the bridging group links one of X², X³. or X⁴ to one of X⁶, X⁷, or X⁸; each R¹, R², R³, R⁴, R⁵, R⁶, and R⁷ are the same or different from each other and are independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, halo, silyl, boryl, phosphino, amino, thioalkyl, thioaryl, and combinations thereof, optionally two or more of R¹, R², R³, and R⁴ on any one ring may be joined to form a fused ring system having up to 50 atoms, not counting hydrogen atoms; and optionally two or more of R⁵, R⁶, and R⁷ on any one ring may be joined to form a fused ring system having up to 50 atoms, not counting hydrogen atoms.

[0152] Embodiment 18: A composition comprising a compound characterized by embodiment 17 and a metal precursor or activated metal precursor.

[0153] Embodiment 19: The composition of any of the above embodiments, wherein the metal precursor characterized by the general formula M(L)_n where M is a metal selected from groups 3-6 of the periodic table of elements and lanthanide elements of the periodic table of elements, each L is a moiety that forms a covalent, dative or ionic bond with M; and n is 1, 2, 3, 4, 5, or 6.

[0154] Embodiment 20: The composition of any of the above embodiments, wherein each L is independently selected from the group consisting of hydrogen, halogen, optionally substituted alkyl, heteroalkyl, allyl, diene, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, aryl, heteroaryl, alkoxy, aryloxy, boryl, silyl, amino, phosphino, ether, thioether, phosphine, amine, carboxylate, alkylthio, arylthio, 1,3-dionate, . oxalate, carbonate, nitrate, sulphate, and combinations thereof, and Lewis base adducts thereof.

[0155] Embodiment 21: The composition of any of the above embodiments, wherein the ligand compound is asymmetrical across the bridging group B.

[0156] Embodiment 22: The composition of any of the above embodiments, wherein the asymmetrical ligand is a result of the selection in the selection of the

C, N, O or S atom, at least, either X¹ and X⁵ are different or X² and X⁶ are different or X³ and X⁷ are different or X⁴ and X⁸ are different.

[0157] Embodiment 23: The composition of any of the above embodiments, wherein the ligand compound is symmetrical across the bridging group.

[0158] Embodiment 24: The composition of any of the above embodiments, wherein R is not hydrogen.

[0159] Embodiment 25: The composition of any of the above embodiments, wherein R¹ is selected from the group consisting of optionally substituted alkyl, heteroalkyl, aryl, and heteroaryl. [0160] Embodiment 26: The composition of any of the above embodiments, wherein — B- in the ligand compound is as defined in either of embodiment 6, 7, 8,

9, 10 or 11.

[0161] Embodiment 27: The composition or complex of any of the above embodiments, wherein M is either Zr, Hf or Ti.

[0162] Embodiment 28: A catalyst formed from the composition or complex of any of the above embodiments and an activator, combination of activators or an activating technique.

[0163] Embodiment 29: A polymerization process comprising subjecting one or more monomers to polymerization conditions in the presence of a catalyst comprising the composition or complex of any of the above embodiments and an activator, combination of activators or an activating technique.

[0164] Embodiment 30: The process of any of the above embodiments, wherein the process is a copolymerization of ethylene and one or more alpha-olefins.

[0165] Embodiment 31 : The process of any of the above embodiments, wherein the one or more monomers is selected from the group consisting of ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, styrene and combinations thereof.

[0166] Embodiment 32: The process of any of the above embodiments, wherein the one or more monomers includes a cyclic olefin.

[0167] Ebodiment 33: A catalyst, complex or compound of any of the above embodiments, were X¹, X², X³ and X⁴ are chosen from Table 1.

[0168] Ebodiment 34: A catalyst, complex or compound of any of the above embodiments, were X^s, X⁶, X⁷ and X⁸ are chosen from Table 2.

Claims

What is claimed is:

1. A metal ligand complex characterized by the formula:

wherein X¹ is N or C, X² is O, S, N(R⁵V or CR⁵, X³ is O, S, N(R⁶)_n» or CR⁶, X⁴ is O, S, N(R⁷)_n- or CR⁷, wherein each n', n'\ and n'" are each independently 0 or 1 , provided that the heteroatom containing ring system is heteroaromatic,

X^s is N or C, X⁶ is O, S, N(R⁵V or CR⁵, X⁷ is O, S, N(R⁶V' or CR⁶, X⁸ is

0, S, N(R⁷V_" or CR⁷, wherein each n', n", and n'" are each independently O or

1, provided that the heteroatom containing ring system is heteroaromatic,"

B is a bridging group linking the heteroaromatic rings and having up to 50 atoms in the bridge not counting hydrogen atoms, provided that the bridging group links one of X², X³, or X⁴ to one of X⁶, X⁷, or X⁸; each R¹, R², R³, R⁴, R⁵, R⁶, and R⁷ are the same or different from each other and are independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, halo, silyl, boryl, phosphino, amino, thioalkyl, thioaryl, and combinations thereof, optionally two or more of R¹, R², R³, and R⁴ on any one ring may be joined to form a fused ring system having up to 50 atoms, not counting hydrogen atoms; and optionally two or more ofR⁵, R⁶, and R⁷ on any one ring may be joined to form a fused ring system having up to 50 atoms, not counting hydrogen atoms;

M is a metal selected from the group consisting of groups 3 through 6 of the Periodic Table of Elements and lanthanides; each L is independently selected from the group consisting of hydrogen, halogen, optionally substituted alkyl, heteroalkyl, allyl, diene, alkenyl, heteroalkenyl, alkynyl, heteroatkynyl, aryl, heteroaryl, alkoxy, aryloxy, boryl, silyl, amino, phosphino, ether, thioether, phosphine, amine, carboxylate, alkylthio, arylthio, 1,3-dionate, oxalate, carbonate, nitrate, sulphate, and combinations thereof; and m" is O, 1, 2, 3, or 4.

2. The metal ligand complex of claim 1 , wherein the complex is characterized by the general formula:

or the general formula

3. The metal ligand complex of claim 2, wherein the complex is characterized by the general formula:

or the general formula

4. The compound of claim 3 , wherein the metal ligand complex is characterized by a formula selected from the group consisting of

5. The compound of claim 3, wherein the metal ligand complex is characterized by a formula selected from the group consisting of

(C)

6. The complex of any of the above claims, wherein B is selected from the group consisting of divalent, optionally substituted alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, aryl, heteroaryl and silyl.

7. The complex of claim 6, wherein the bridging group B is substituted with one or more optionally substituted hydrocarbyl or heteroatom- containing hydrocarbyl groups.

8. The complex of any of the above claims, wherein B is represented by the general formula -{Q"R⁴⁰ ₂-_z")_z — wherein each Q" is independently either carbon or silicon and wherein each R⁴⁰ substituent is independently selected from the group consisting of hydrogen and optionally substituted hydrocarbyl and heteroatom containing hydrocarbyl, wherein two or more R ° substituents are optionally joined into a ring structure having from 3 to 50 atoms in the ring structure not counting hydrogen atoms; z' is an integer from 1 to 20; and z" is 0, 1 or 2.

9. The complex of any of the preceeding claims, wherein -B- is selected from the group consisting of

wherein each Q is independently selected from the group consisting of carbon and silicon, each R⁶⁰ is independently selected from the group consisting of hydrogen and optionally substituted hydrocarbyl and heteroatom containing hydrocarbyl, provided that at least one R⁶⁰ substituent is not hydrogen, wherein the R⁶⁰ substituents are optionally joined into a ring structure having from 3 to 50 atoms in the ring structure not counting hydrogen atoms, and m' is 0, 1, or 2.

10. The complex of any of the above claims, wherein -B- is selected from the group consisting Of-(CH₂)-, -(CH₂)₂-, -(CH₂)3-₅-(CH₂)₄-_;i -(CH₂)₅-, -(CH₂)₆-,-(CH₂)₇-, -(CHa)₈-, -(CH(CH₃))-, -(CH(CH₃))₂-, -(C(CH₃)₂)-, -(C(CH₃)₂)₂-, -(C(CH₃)₂)₃-, -CH₂CH(CH₃)CH₂-, -CH₂C(CH₃)₂CH₂-, -CH₂CH(C₆H₅)CH₂-, -CH(CH₃)CH₂CH(CH₃)-, -CH(C₂H₅)CH₂CH(C₂H₅)-,

-CH(CH₃)CH₂CH₂CH(CH₃H -CH(C₆H₅)CH₂CH(C₆H₅K -CH(C₆H₅)CH₂CH(C₆H₅)-, -(C₆H₄)CH₂CH₂(C₆H₄)-, -(C₆H₄)CH₂CH₂CH₂(C₆H₄)-, -(C₆H₄)CH₂CH₂CH₂CH₂(C₆H₄)-,

11. The complex of any of the above claims, wherein -B- is represented by the formula

where (Q"R⁴⁰ _2-Z")z' is defined in claim 8 and wherein each R⁸⁰ substituent is independently selected from the group consisting hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, halo, silyl, boryl, phosphino, amino, thioalkyl, thioaryl, and combinations thereof, optionally two or more of R⁸⁰ groups on any one ring may be joined to form a fused ring system having up to 50 atoms, not counting hydrogen atoms.

12. The complex of any of the above claims, wherein the complex is asymmetric across the bridging group.

13. The complex of claim 12, wherein the complex is asymmetrical in the selection of the C, N, O or S atoms in the heterocycle rings such that, at least, either X¹ and X^s are different or X² and X⁶ are different or X³ and X⁷ are different or X⁴ and X⁸ are different.

14. The complex of any of the above claims, wherein the complex is symmetric across the bridging group B.

15. The complex of any of the above claims, wherein R¹ is not hydrogen.

16. The complex of any of the above claims, wherein R¹ is selected from the group consisting of optionally substituted alkyl, heteroalkyl, aryl and optionally substituted aryl.

17. A compound characterized the formula:

wherein X¹ is N or C, X² is O, S, N(R⁵)_n- or CR⁵, X³ is O₅ S, N(R V or CR⁶, X⁴ is O, S, N(R⁷)_n>_" or CR⁷, wherein each n', n", and n'" are each independently 0 or 1, provided that the heteroatom containing ring system is heteroaromatic,

X⁵ is N or C, X⁶ is O, S, N(R⁵V or CR⁵, X⁷ is O, S, N(R⁶)_n- or CR⁶, X^s is

0, S, N(R⁷)n— or CR⁷, wherein each n', n", and n'" are each independently 0 or

1 , provided that the heteroatom containing ring system is heteroaromatic;

B is abridging group linking the heteroaromatic rings and having up to 50 atoms in the bridge not counting hydrogen atoms, provided that the bridging group links one of X², X³, or X⁴ to one of X⁶, X⁷, or X⁸; each R¹, R², R³, R⁴, R⁵, R⁶, and R⁷ are the same or different from each, other and are independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, halo, silyl, boryl, phosphino, amino, thioalkyl, thioaryl, and combinations thereof, optionally two or more of R¹, R², R³, and R⁴ on any one ring may be joined to form a fused ring system having up to 50 atoms, not counting hydrogen atoms; and optionally two or more of R⁵, R⁶, and R⁷ on any one ring may be joined to form a fused ring system having up to 50 atoms, not counting hydrogen atoms.

18. A composition comprising a compound characterized by claim 17 and a metal precursor or activated metal precursor.

19. The composition of claim 18, wherein the metal precursor characterized by the general formula M(L)_n where M is a metal selected from groups 3-6 of the periodic table of elements and lanthanide elements of the periodic table of elements, each L is a moiety that forms a covalent, dative or ionic bond with M; and n is 1, 2, 3, 4, 5, or 6.

20. The composition of claim 19, wherein each L is independently selected from the group consisting of hydrogen, halogen, optionally substituted alkyl, heteroalkyl, allyl, diene, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, aryl, heteroaryl, alkoxy, aryloxy, boryl, silyl, amino, phosphino, ether, thioether, phosphine. amine, carboxylate, alkylthio, arylthio, 1,3-dionate, oxalate, carbonate, nitrate, sulphate, and combinations thereof, and Lewis base adducts thereof.

21. The composition of claim 18, wherein the ligand compound is asymmetrical across the bridging group B.

22. The composition of claim 21, wherein the asymmetrical ligand is a result of the selection in the selection of the C, N, O or S atom, at least, either X¹ and X⁵ are different or X² and X⁶ are different or X³ and X⁷ are different or X⁴ and X⁸ are different.

23. The composition of claim 18, wherein the ligand compound is symmetrical across the bridging group.

24. The composition of any of the above claims, wherein R¹ is not hydrogen.

25. The composition of any of the above claims, wherein R¹ is selected from the group consisting of optionally substituted alkyl, heteroalkyl, aryl, and heteroaryl.

26. The composition of any of the above claims, wherein -B- in the ligand compound is as defined in either of claims 6, 7, 8, 9, 10 or 11.

27. The composition or complex of any of the above claims, wherein M is either Zr, Hf or Ti.

28. A catalyst formed from the composition or complex of any of the above claims and an activator, combination of activators or an activating technique.

29. A polymerization process comprising subjecting one or more monomers to polymerization conditions in the presence of a catalyst comprising the composition or complex of any of the above claims and an activator, combination of activators or an activating technique.

30. The process of claim 29, wherein the process is a copolymerization of ethylene and one or more alpha-olefins.

31. The process of claim 30, wherein the one or more monomers is selected, from the group consisting of ethylene, propylene, 1-butene, 1-hexene, 1- octene, 1-decene, styrene and combinations thereof.

32. The process of claim 29, wherein the one or more monomers includes a cyclic olefin.