WO1999041290A1 - Catalyst compounds with beta-diiminate anionic ligands and processes for polymerizing olefins - Google Patents

Abstract

The present invention relates to catalyst systems, processes for making such catalysts, intermediates for such catalysts, and olefin polymerization processes using such catalysts wherein such catalyst includes a component represented by formula (I), optionally (a), wherein, R and R' independently represent a hydrogen atom, or a substituted or unsubstituted, branched or unbranched hydrocarbyl or organosilyl radical; R?1, R2 and R3¿ independently represent a hydrogen atom, or a substituted or unsubstituted, branched or unbranched hydrocarbyl radical; and M is a group IIIB, IVB, VB, VIIB or VIII transition metal; T independently represents a univalent anionic ligand such as a hydrogen atom, or a substituted or unsubstituted hydrocarbyl, halogeno, aryloxido, arylorganosilyl, alkylorganosilyl, amido, arylamido, phosphido, or arylphosphido group, or two T groups taken together represent an alkylidene or a cyclometallated hydrocarbyl bidentate ligand; L independently represents a sigma donor stabilizing ligand; X, which is optional, represents a relatively weakly coordinated anion; and a = 0 to 4 inclusive, b = 0 to 4 inclusive, provided a+b≤4.

Description

CATALYST COMPOUNDS WITH BETA-DIIMINATE ANIONIC LIGANDS AND PROCESSES FOR POLYMERIZING OLEFINS

FIELD OF THE INVENTION

5 The present invention relates to catalyst systems, processes for making such catalysts, intermediates for such catalysts, and olefin polymerization processes using such catalysts.

BACKGROUND OF THE INVENTION

10 Olefin polymers are useful as plastics for packaging materials, molded items, films, etc., and as elastomers for molded goods, industrial belts of various types, tires, adhesives. and other uses. It has been well known in the art that the structures of olefin polymers, and hence their properties and capability of use, are highly dependent on the catalyst used during their

15 synthesis. Therefore, as the potential applications for polymers have changed and developed over the past years so too has the need for new and more catalyst systems and improved polymerization processes utilizing such catalysts become necessary.

20 SUMMARY OF THE INVENTION

In accordance with the present invention, there is provided a novel catalyst system for the polymerization of olefins, said catalyst system including a transition metal complex of a β-diiminate bidentate ligand.

There is also provided in accordance with the present invention a novel 25 catalyst compound component for the polymerization of olefins, said compound being represented by Formula (I), as follows:

(I) ⁾b

optionally

wherein

R and R' independently represent a hydrogen atom, or a substituted or unsubstituted, branched or unbranched hydrocarbyl or organosilyl radical;

R¹, R², and R³ independently represent a hydrogen atom, or a substituted or unsubstituted, branched or unbranched hydrocarbyl radical; and M represents a group IHB, IVB, VB, VLB, VHB or VLϋ transition metal; each T independently represents a univalent anionic ligand such as a hydrogen atom, or a substituted or unsubstituted hydrocarbyl, halogeno, aryloxido, arylorganosilyl, alkylorganosilyl, amido, arylamido, phosphido, or arylphosphido group, or two T groups may together or other anionic ligands such as an alkylidene or a cyclometallated hydrocarbyl radical; each L independently represents a sigma donor stabilizing ligand or one L together with one T may together represent a second β- diiminate ligand represented by Formula (LT) (below);

X, which is optional, represents a relatively weakly coordinated anion; and 3

a = an integer from 0 to 4 inclusive, b = an integer 0 to 4 inclusive, provided a+b < 4.

Further provided in accordance with the present invention is a novel process for the polymerization of olefins. The process provides for the polymerization of one or more olefins in the presence of a homogeneous catalyst comprising a catalyst represented by Formula (I) or a heterogeneous catalyst system comprising a Formula (I) catalyst and one or more co-catalysts.

The present invention also provides for a novel process of making a catalyst component represented by Formula (I) by contacting a group TTTB, rVB, VB, VLB, VLLB or VLTI transition metal containing compound with a compound containing a β-diiminate ligand represented by the following Formula (II), in particular a compound represented by Formula (LU) (below): π

R R

/

^■N

R³ ( Θ

\

R2 R

m

R1> R

/

^■N

R m

^■N

\

R2 R'

wherein

R, R', R¹, R² and R³ have the same meanings stated above; and m represents a group that is readily displaced by a transition metal, for example hydrogen or a group comprising a group IA or LIA metal.

BRIEF DESCRIPTION OF THE DRAWINGS

Fig. 1 depicts the crystal structure of the (Ph) nacnacTiCl (THF)₂, prepared in

Example IA.

Fig. 2 depicts the crystal structure of the (Ph)₂nacnacVCl₂(THF)₂, prepared in

Example IB. Fig. 3 depicts the crystal structure of the (Ph)₂nacnacCrCl₂(THF) , prepared in

Example IC.

Fig. 4 depicts the crystal structure of the (Ph)₂nacnacVMe₂, prepared in

Example 3A.

Fig. 5 depicts the crystal structure of the (Ph)₂nacnacVMe(Et₂O)(THF)[B(C₆H₃(CF₃)₂)₄], prepared in Example 5A

(BArF anion not depicted). 5

Fig. 6 depicts the crystal structure of the ((Ph)₂nacnac)₂Cr, prepared in Example 6.

DETAILED DESCRIPTION OF THE INVENTION Herein certain terms are used to define certain chemical groups and compounds. These terms are defined below.

"alkyl metal" or "metal alkyl" refer to a compound having an alkyl radical bound directly to a metal. For example, an alkyl metal (or metal alkyl) would include alkyl aluminum (or aluminum alkyl). "group IA, LA, LLB, -TJA, LLTB, IVB, VB, VLB, VUB or VLLL" refers to the metals within the respective group number of the Periodic Table of the

Elements (CRC Handbook of Chemistry and Physics, 78^th ed. 1997-1998).

For example, group LVB would include titanium, zirconium, etc. and group

Vm would include palladium, platinum, cobalt, etc. "hydrocarbyl" refers to a univalent group containing only carbon and hydrogen. If not otherwise stated, hydrocarbyl as used herein preferably contains 1 to about 30 carbon atoms.

"linear α-olefin" refers to an olefin, defined below, wherein R¹⁰ represents a hydrogen atom or an n-alkyl. If not otherwise stated, linear α- olefin as used herein preferably contains 2 to about 12 carbon atoms.

"olefin" refers to a compound of formula CH₂=CHR¹⁰, wherein R¹⁰ represents a hydrogen atom or n-alkyl or branched alkyl, preferably hydrogen or n-alkyl.

"organosilyl" refers to a univalent group containing at least one carbon to silicon bond. One example is trimethylsilylmethyl.

"Polymerization" refers to a process that produces polymers, copolymers, teφolymers, etc. that generally have a degree of polymerization of at least about 20 or more. However, the process is also useful to produce oligomers of a lower degree of polymerization. "saturated hydrocarbyl" refers to a hydrocarbyl radical that is free from double or triple bonds, also referred to as unsaturated bonds. Examples of such groups include alkyl and cycloalkyl.

"substituted hydrocarbyl" refers to a hydrocarbyl radical that contains one or more substituent groups.

"transition metals" refers generally to the group LTLB, VB, VB, VLB, VLTB or VLLJ transition metals. If not otherwise stated, transition metals as used herein preferably includes the group IVB, VB, or VLB transition metals, "unsaturated hydrocarbyl" refers to a hydrocarbyl radical that contains one or more double or triple bonds. Examples of such groups include olefinic, acetylenic, or aromatic groups.

"unsubstituted hydrocarbyl" refers to a hydrocarbyl radical that contains no substituent groups.

The present invention concerns catalysts and polymerization processes for olefins in the presence of various homogenous transition metal catalysts complexed with at least one β-diiminate bidentate ligand or a catalyst systems comprising at least one such transition metal catalyst with one or more co- catalysts. The β-diiminate ligand may be represented by Formula (II), as follows: π

Rⁱs R

/

^•N

R³ ( Θ

\

R2 R wherein

R, R', R¹, R² and R³ have the meanings stated above; and said transition metal also has bound to it a ligand that may be displaced by said olefin or added to said olefin.

The following Reaction Scheme 1 details one way of synthesizing a β- diiminate precursor compound corresponding to the β-diiminate monoanionic ligand, represented by Formula (LI). This synthesis reaction is further discussed in the journal articles by S.G. McGeachin Canadian J. of Chem. v.46, pp.1903-1912 (1968) and T. Potesil and H. Potesilova, J. of Chromatogr., v.312, pp. 387- 393 (1984), the disclosures of which are hereby incoφorated by reference. It will be appreciated from this series of transformations that the β-diimine compound can readily be prepared with different groups on each of the nitrogen atoms by utilizing two different substituted amines in the reaction sequence. By analogy to the familiar "acac" nickname for the acetylacetonato moiety, the nickname "nacnac" will be used herein to refer to the 2,4-pentane diiminato moiety, represented by Formula (U). For example, the hydrogen or lithium bridged diimine structures in the last two steps of Reaction Scheme 1 may be represented herein as nacnacH and nacnacLi, respectively. The nacnac terminology used herein may further include a prefix indicating the type of radical group present in the R and R' positions, for instance, "Me" to represent methyl or "Ph" to represent phenyl (e.g., (Ph)(Me)nacnacH or (Ph)₂nacnacH).

_D RN_TrHτ-, ^N ii ^R O n D ^ E^cι3O+B ^aF^s Λ,- N I RH N I,R^~Η^~| I

2) R'NH2

R. ^U \ _^R' R ,H. _^R ' y Base

.R '

N N' Meli N ^{' •}N ^'

Reaction Scheme 1: Synthesis of β-Diiminates ((R)(R')nacnacLi)

The catalyst compound of the present invention may be prepared in a variety of ways, using techniques and, in addition to the novel β-diimine compounds and corresponding monoanionic β-diiminate ligands, known precursors for the cationic and anionic portions of the catalyst compound. The catalyst compound of the present invention may be formed either beforehand or in situ (i.e., in the vessel in which the polymerization is to take place).

The β-diimine compounds of Formula (UL), which may serve as precursors for the monoanionic bidentate ligand, represented by Formula (LT), can be reacted with a transition metal compound to form a catalyst compound, as represented by Formula (I), that is useful for the polymerization of olefins.

In a preferred form of the β-diimine compounds of Formula (ELI), the hydrogen or metal containing group represented by m includes hydrogen or a group LA metal, in particular, lithium, sodium or potassium.

Useful transition metal containing compounds for forming such catalyst compounds include those which comprise a group LLLB, LVB, VB, VLB, VLLB or VLH transition metal having ligands that may be displaced by the monoanionic bidentate ligand derived from the β-diimine precursor 9

compound. Particularly suitable transition metal containing compounds include transition metal salts having ligands, in addition and/or including those represented by T and L of Formula (I), that are readily displaceable by the ligand derived from the diimine precursor compound under conditions that do not adversely affect either the transition metal compound or ligand adducts thereof. These transition metal salts include transition metal halides (such as dichloride, trichloride or tetrachloride, with trichloride being preferred), transition metal carboxylates (such as acetates), transition metal alkoxides (such as methoxides), or transition metal sulfonates (such as triflates or tosylates). Typically, these catalyst may be formed in the presence of a suitable solvent. Suitable solvents include Lewis bases such ethers, thioethers, amines or nitriles with diethylether and tetrahydrofuran being preferred. In addition, a metal alkyl including, in particular, metal alkyls having a group IA, LLA or ILTA metal such as lithium alkyls (such as alkyl methyl lithium, ethyl lithium, n-propyl and/or i-propyl lithium, n-butyl, or t-butyl lithium), aluminum alkyls, preferably including aluminum trialkyls (such as trimethyl aluminum, triethyl aluminum, triisobutylaluminum or trioctyl aluminum), Grignard reagants and the like may be simultaneously reacted with the other reactants to form the desired catalyst compound. Alternatively, a compound comprising the β-diiminate ligand, such as those represented by Formula (I), can be subsequently reacted with such metal alkyls to form the desired catalyst compound or a compound of Formula (I) can be reacted in situ and/or in the presence of an olefin to provide a catalyst having the desired activity.

With respect to the catalyst compounds represented by Formula (I), above, the relatively weakly coordinated anion X, when present, may be any suitable anion known for this puφose. Suitable anions are often bulky anions, particularly those that delocalize their negative charge. X, in Formula (I), preferably represents tetrakis [3,5-bw(trifluoromethyl)phenyl]borate (herein 10

referred to as BArF), (phenyl)₄B\ (C₆F₅)₄B^", (CH₃)(C₆F₅)₃B^", PF6^", BF₄\ SbF₆ ^" , trifluoromethanesulfonate ( herein referred to as triflate or OTf ), and p- toluenesulfonate (herein referred to as tosylate or OTs^"). Preferred weakly coordinating anions include BArF^" and (C₆F₅) B. Catalyst compounds of Formula (I) wherein the weakly coordinated anion is present may be made by further reacting a compound of Formula (I) having at least one alkyl group, with about one equivalent of a strong acid, the conjugate base of which is a non-coordinating anion such as noted for X above, in the presence of a suitable solvent. Suitable solvents include, for example, methylene chloride, hexane, benzene, toluene, chlorobenzene, diethyl ether and the like.

The substituent groups represented by R, R', R¹, R² and R³ should be selected so that they do not substantially interfere or impede the particular type of polymerization reaction for which the catalyst is designed. Whether a particular group is likely to interfere can initially be judged by one skilled in the art based on the parameters of the process where the catalyst will be employed. For instance, in polymerization processes where an alkyl aluminum compound is used, catalyst containing an active (relatively acidic) hydrogen atom, such as hydroxyl or carboxyl may not be suitable because of the known reaction between alkyl aluminum compounds and such active hydrogen containing groups (but such polymerization processes may still be possible if enough "extra" alkyl aluminum compound is added to react with these groups). However, in very similar polymerization processes where alkyl aluminum compounds are not present, these groups containing active hydrogen may be present. An important factor to consider in determining the operability of compounds containing any particular functional group are the effect of the group on the coordination of the metal atom, and side reactions of such a group with other process ingredients, such as those noted above. Therefore, of course, the further away from the metal atom the functional group is, the less 11

likely it is to influence, say, a polymerization. If there is doubt as to whether a particular functional group, in a particular position, will affect a reaction, simple minimal experimentation will provide the requisite answer.

In a preferred form of Formulas (I), R and R' independently represent a hydrogen atom, or an alkyl, aryl, alkylaryl, arylorganosilyl, or alkylorganosilyl radical. Preferably, R and R' will independently include such radicals wherein the carbon atom, directly bound to the nitrogen, has at least two carbon atoms bound thereto, for example, isopropyl, phenyl, 2,6- isopropylphenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 4-methylphenyl,

2,4,6-trimethylphenyl or 2-t-butyl phenyl. R¹, R², and R³ independently represent a hydrogen atom or a hydrocarbyl radical, preferably a hydrogen atom or an alkyl radical having 1-6 carbon atoms, and more preferably a hydrogen atom or methyl radical. M represents a group IVB, VB or VLB transition metal, preferably, chromium, vanadium or titanium. These variables defining the preferred forms of the compounds represented by Formula (I) are equally applicable, when present, to the preferred forms of the β-diiminate ligand and β-diiminate compound represented by Formula (LI) & (LU), respectively.

Exemplary hydrocarbyl groups for T, in Formula (I), include methyl, ethyl, propyl, butyl, amyl, isoamyl, hexyl, iso-butyl, heptyl, octyl, nonyl, decyl, cetyl, 2-ethylhexyl, phenyl and the like, with methyl being preferred. Exemplary halogeno groups for T include chloro, bromo, fluoro, and iodo, with chloro being preferred. Exemplary alkoxido and aryloxido groups for T include methoxido, ethoxido, phenoxido and substituted phenoxido's. Exemplary amido groups for T include dimethylamido, diethylamido, methylethylamido, di-t-butylamido, diisopropylamido and the like. Exemplary arylamido groups for T include diphenylamido and other substituted phenyl 12

amido's. Exemplary phosphido groups for T include diphenylphosphido, dicyclohexylphosphido, diethylphosphido, dimethylphosphido and the like. Exemplary alkylidene anionic ligands, for two T groups taken together, include methylidene, ethylidene and propylidene.

Each L in the above Formula (I) can represent any suitable electron donor ligand. Suitable ligands include those containing an atom, such as oxygen, nitrogen, phosphorous or sulfur, which has a non-bonded electron pair. Examples of these ligands include, but are not limited to, ethers, amines, phosphines and thioethers. Ethers such as tetrahydrofuran (THF) and amines such as pyridine are preferred, with THF being particularly preferred.

In a preferred form of the catalytic compound represented by Formula (I), a and b independently represent integers from 0 to 3, inclusive. More preferably, a and b independently represent either 0 or 2. It will be appreciated that when Formula (I) is meant to characterize a mixture of two or more catalytic compounds whereby a and b represent an average of the a and b values of the catalytic compounds, a and b may independently represent any number from 0 to 4, including 1.2 to 1.8.

The polymerization reaction using the catalyst of the present invention may be carried out with a catalyst compound represented by Formula (I) either by itself, referred to as a homogenous catalyst system, or with one or more co- catalysts. The catalyst and or co-catalysts may initially be in a solid state or in solution. The olefin and/or olefins may be in the gas or liquid state (including gas dissolved in a solvent). A liquid, which may or may not be a solvent for any or all of the reactants and/or products may also be present. Suitable liquids include alkanes, cycloalkanes, halogenated alkanes and cycloalkanes, 13

and ethers. Solvents that are especially useful include methylene chloride, hexane, toluene, dichlorobenzene, and benzene.

Co-catalysts useful in the practice of the present invention are group LLA, LLB, LLA and LLLB metal alkyls having at least one alkyl group, preferably an alkyl group having 1 to 8 carbon atoms, bonded to the metal. Suitable metal alkyls include dialkyl magnesium, dialkyl zinc, trialkyl boranes, triarylboranes and aluminum alkyls. Suitable aluminum alkyls include trialkylaluminums (such as trimethylaluminum, triethylaluminum, triisobutylaluminum, and trioctylaluminum). Trialkylaluminums with alkyl groups of four carbons or greater are preferred. Other aluminum alkyls useful in the practice of the present invention include alkylaluminum alkoxides (such as diethylaluminum ethoxide and ethylaluminum diethoxide), and alkylaluminum halides (such as diethylaluminum chloride, diethylaluminum bromide, diethylaluminum iodide, diethylaluminum fluoride, ethyl aluminum dichloride, ethyl aluminum dibromide, ethyl aluminum diiodide, ethyl aluminum difluoride and ethyl aluminum sesquichloride). Suitable triarylboranes include those that are fluorine substituted (such as tripentafluorophenyl borane).

Other suitable aluminum alkyls are aluminoxanes including those represented by the general formula (R"-Al-O)_n for the cyclic form and R"(R"- Al-O)_n-Al(R")₂ for the linear form. In these formulas, R" independently represents an alkyl group (such as methyl, isopropyl, butyl and the like) preferably with more than two carbon atoms, more preferably with 3-5 carbon atoms, and n is an integer, preferably from about 1 to about 20. Most preferably, R includes a methyl or isobutyl group. Mixtures of linear and cyclic aluminoxanes useful in this invention include, but are not limited to, ethyl aluminoxanes, isobutyl aluminoxane, and methyl aluminoxane. 14

The preferred metal alkyl co-catalysts generally include aluminoxanes and trialkylaluminum. When a co-catalyst is used, the mole ratio of the metal alkyl co-catalyst to catalyst should be from about 1 : 1 to about 1000: 1. The preferred mole ratio being from about 10: 1 to about 200: 1.

The catalyst system of the present invention may be used in either slurry or gas phase polymerization processes. After catalysts have been formed, the polymerization reaction is conducted by intermixing the monomer charge with a catalytic amount of the catalyst at a temperature and at a pressure sufficient to initiate the polymerization reaction. If desired, an organic solvent may be used as a diluent and to facilitate materials handling. The polymerization reaction is carried out at temperatures of from about -100°C up to about 200°C, depending on the operating pressure, the pressure of the entire monomer charge, the particular catalyst being used, and its concentration. Preferably, the temperature is from about 20°C to about 135°C. The pressure can be any pressure sufficient to initiate the polymerization of the monomer charge. For instance, the pressure may range from atmospheric up to about 1000 psig. As a general rule, a pressure of about 20 to about 800 psig is preferred.

When the catalyst is used in a slurry-type process, an inert solvent medium is used. The solvent should be one which is inert to all other components and products of the reaction system, and be stable at the reaction conditions being used. It is not necessary, however, that the inert organic solvent medium also serve as a solvent for the polymer produced. The inert organic solvents which may be used include saturated aliphatic hydrocarbons (such as hexane, heptane, pentane, isopentane, isooctane, purified kerosene and the like), saturated halogenated alkanes (such as dichloromethane, 15

choloroform and the like) saturated cycloaliphatic hydrocarbons (such as cyclohexane, cyclopentane, dimethylcyclopentane, and the like), aromatic hydrocarbons (such as benzene, toluene, xylene and the like). Particularly preferred solvents are dichloromethane, toluene, cyclohexane, hexane, benzene and heptane.

When the catalyst is used in a gas phase process, it may be suspended in a fluidized bed with, e.g., ethylene. Temperature, pressure and ethylene flow rates are adjusted so as to maintain acceptable fluidization of the catalyst particles and resultant polymer particles.

The catalyst of the present invention may be employed on a solid catalyst support (as opposed to just being added as a solid or in solution), for instance on silica gel or any other suitable catalyst support that does not adversely affect the performance of the catalyst. By supported is meant that the catalyst may simply be carried physically on the surface of the solid support, may be adsorbed, absorbed, or carried by the support by other means.

Preferred olefins and cycloolefins in the polymerization include at least one or more of the following monomers: ethylene, propylene, 1-butene, cyclopentene, 1-hexene; with ethylene and mixtures of ethylene with propylene and/or 1-hexene being more preferred. Ethylene alone is especially preferred. Oligomers may also be used, with or without a co-monomer. As may be desired, more than one monomer may be employed in which case a copolymer will be the likely product obtained. However, depending on the reactants employed and the given reaction conditions, polymerization may not always occur. 16

EXAMPLES

The following examples are given as particular embodiments of the invention and to demonstrate the practice and advantages thereof. It is understood that the examples are given by way of illustration and are not intended to limit the specification or the claims that follow in any manner.

In preparation of the following catalysts, all manipulations were performed under vacuum using glove box or Schlenk techniques. The chemicals are commercially available from sources such as Strem Chemical

Co. and Aldrich Chemical Co. Methylaluminoxane (MAO), unless otherwise noted, was used as a 10 wt. in toluene solution. Methyl lithium (MeLi) was used as a 1.4M solution or as a solid obtained by evaporation of the solvent. Aniline and Aniline-^ (C₆D₅NH₂) was freshly distilled just prior to use. Trimethylsilylmethyllithium was supplied as a 1.0M solution in pentane and crystallized as a white crystalline solid from solution at -30°C prior to use. Benzene-όfe (C D₆) and Tetrahydrofuran-<i_s (THF--ig) were pre-dried with Na and stored under vacuum over a Na/K alloy prior to use. Pyridine-6?₅ (pyr-ds) and Dichloromethane--i₂ (CD₂C1₂) were dried with CaH₂ and vacuum distilled onto pre-activated 4 A molecular sieves prior to use. Pentane, Diethylether,

Tetrahydrofuran (THF), and Hexamethyldisiloxane (HMDS) were dried over Na/benzophenone prior to use.

Trichloro t (tetrahydrofuran) vanadium (VC1₃(THF)₃) and Trichloro tra(tetrahydrofuran) titanium (TiCl₃(THF)₃) are prepared from the corresponding metal trichloride (TiCl and VC1₃, respectively) by reaction with anhydrous tetrahydrofuran as noted in the article by Manzer, L.E. Inorganic Synthesis Vol. XXI, pp. 135-140, John Wiley & Sons (1982) the complete disclosure of which is hereby incoφorated by reference. 17

Trichloro trw(tetrahydrofuran) chromium (CrCl₃(THF)₃) is prepared by converting anhydrous chromium trichloride into its tetrahydrofuranate by continuous extraction with anhydrous tetrahydrofuran of its solid form admixed with catalytic amounts of zinc dust as noted in the article by Herwig,

W.; Zeiss, H.H, Journal of Organic Chemistry Vol. 23, p. 1404 (1958) ) the complete disclosure of which is hereby incoφorated by reference.

The crystalline oxonium acid [(3,5-(CF₃)₂C₆H₃)₄B]^"[H(OEt₂)₂]⁺ is synthesized by exposing a solution of Na[(3,5-(CF₃)₂C₆H₃)₄B] in ether to HCl and isolating the [(3,5-(CF₃)2C₆H₃)₄B]^"[H(OEt2)2]⁺. This synthesis is discussed in the article by Brookhart, M.; Grant, B.; Volpe, A.F., Organometallics Vol. 1 1, No. 1 1, pp. 3920-3922 (1992).

Analytical Procedures:

NMR spectra were recorded using one or more of the following spectrometers Bruker AM-250, WM-250 or 400; chemical shifts were referenced to the residual proton resonance of the deuterated solvent indicated.

Fourier Transform Infra Red spectra were recorded on a Mattson Alpha

Centauri spectrometer with a resolution of 4 cm^" .

UV-VIS spectra were recorded using a Bruins Omega 20 spectrophotometer and a Beckman DU 640 spectrometer.

Mass spectra were obtained from the University of Delaware Mass Spectrometry Facility. 18

Elemental analyses were performed either by Oneida Research Services, Whiteboro, NY 13492 or Schwarzkopf Microanalytical Laboratory, Woodside, N.Y. 11377. Note: the elemental analyses for Examples 1 A and IB did not fit the calculated values, presumably, due to the loss of the coordinated solvents resulting from vigorous pumping under high vacuum.

Room temperature magnetic susceptibilities were determined using a

Johnson-Matthey Magnetic Susceptibility Balance which utilizes a modification of the Gouy method. The molar magnetic susceptibility was corrected for diamagnetism using Pascal constants and the effective magnetic moment (U_eff) was calculated from the expression: μ_€ff = 2.828 (Tχrn where T is the temperature in Kelvin and χm is the molar magnetic susceptibility corrected for diamagnetism.

Preparation of 2-N-Phenylamino-4-N^,-PhenvIimino-2-Pentene,

(Ph)?nacnacH

In a flask, re-distilled aniline was mixed with a molar equivalent (eq.) of 2,4-pentanedione and benzene were mixed. The mixture was boiled on an oil-bath and the distilled-off azeotropic mixture (benzene-water) was replaced with benzene until all water was separated. Then, the suφlus solvent was removed by distillation. The crude product was re-distilled in vacuo (boiling point approx.75°C) to give a crystalline substance which was re-crystallized from n-hexane to yield fine yellowish crystals of 2-N-phenylamido-2'-penten-

4-one.

These 2-N-phenylamido-2'-penten-4-one yellow crystals were then used to prepare (Ph)₂nacnacH in accordance with the Reaction Scheme 1 19

(above). A molar eq. of triethyloxonium tetrafluoroborate in dichloromethane was added dropwise to the 2-N-phenylamido-2'-penten-4-one in the same solvent. The mixture was allowed to stand for 30 minutes. Then, 1 molar eq. of aniline in dichloromethane was added. After 1 hour the solvent was removed completely in vacuo and the residual oil was dissolved in hot ethyl acetate and the 2-N-phenylamino-2'-penten-4-phenylimmonium tetrafluoroborate product was allowed to crystallize.

The free base of the ligand, (Ph)₂nacnacH was prepared from the cationic salt, 2-N-phenylamino-2'-penten-4-phenylimmonium tetrafluoroborate. An equimolar reaction with potassium hydride (KH) (optionally MeLi) resulted in about a 98% yield of yellow neutral, deprotonated, (Ph)₂nacnacH crystals. Alternatively, a metal salt, for instance (Ph)₂nacnacLi (or (Ph)₂nacnacK), could have been formed from the 2-N- phenylamino-2'-penten-4-phenylimmonium tetrafluoroborate cation salt and two equivalents of MeLi (or KH). Deuterated versions of these compounds are formed by substituting aniline-^ for unlabeled aniline.

EXAMPLE IA Preparation of 2,4-pentane di(N-phenyl)iminato dichioro bis- tetrahydrofuran titanium, (Ph)₂nacnacTiCI₂(THF)₂ and the Corresponding Compound with the Deuterated Ligand, (Ph-rfs^nacnac:

1.50 g (6.0 mmoles) of (Ph)₂nacnacH was dissolved in 50 ml of THF and cooled to -30°C. 1 equivalent (132 mg) of MeLi was slowly added as a solid with stirring. The resulting (Ph)₂nacnacLi was added dropwise over a three hours period, to a cooled 2.223 g (6.0 mmole) solution of TiCl (THF)₃ in 150 ml of THF. The color of the solution changed from sky blue to brown, then to dark brown. The reaction mixture was concentrated to 50 ml, and cooled to -30°C for crystallization. A dark brown microcrystalline powder 20

was isolated by filtration and washed with cold THF several times. After drying under vacuum, 2.92 g (95% yield) of (Ph)₂nacnacTiCl₂(THF)₂ as microcrystalline brown compound was isolated.

The resulting compounds were analytically tested and the results are shown in Tables 1A.1-3. The single crystal X-ray diffraction results are shown in Fig. 1.

21

TABLE 1A.1

ANALYTICAL DATA FOR

(Ph)₂nacnacTiCl₂(THF)₂ (Ph-rf₅)₂nacnacTiCl₂(THF)₂

Η NMR (CD₂Cl₂)^a: 103.1 89.5 11.4 6.25 3.65 3.27 1.61 δ (ppm) (6H,b) (lH,b) (2H) (4H) (8H) (2H) (8H)

'H NMR (THF-d₈)^a: 27.07 12.79 8.07 3.95 3.31 #** *** δ (ppm) (6H) (1H) (4H) (4H) (2H)

Η NMR (THF-d₈)^a: ^f 108.76 85.80 *** *#* **# *** *** δ (ppm) (6H) (1H)

²H NMR (TΗF)^a: 16.1 15.4 6.1 *** *** *** *** δ (ppm) (4D) (2D) (4D)

IR - KBr^b: (cm^-1): 3053m 2971s 2928m 2876m 1591m 1534s 1483s

1447m 1359s 1290m 1263s 1 185w 1066w 919m

840s 761m 709s 518w 447w *** ***

IR - KBr^b: (cm^"1): ^τ 2969m 2928m 2890m 2876m 227 l w 1575m 1530m

1432m 1369vs 1298vs 1250w 1 147 1015m 875m

852m 824w 769 557m 464w ##* ***

Mass Spectrometry: 367 (100.0) [M⁺ - (THF)₂ 31 1.8 (3.1) [M⁺ - C1(THF)₂] m/z (%)

Mass Spectrometry: 377.03 (100.0) [M⁺ - (THF)₂] 342.06 (3.4) [M⁺ - C1(THF)₂] M/z (%)

UV-vis (THF) ^c: 517 (493.6 M^"1 cm^"1) 445 (2383.9 M^'1 cm^"1) λma (ε) μ-fr 2.0(std. dev. 1), μ_B (294K)

Melting Pt. Range: 154 - 159°C

C₂ H_MN,0₂TiCl₂

Calculated: (%) C 58.69 H 6.51 N 5.48

Measured: (%)

Sample 1 C 56.86 H 5.89 N 3.77

Sample 2 C 57.36 H 6.51 N 5.52

Table Notes: (Applicable for Tables 1A-6)

⁺- indicates analytical results for corresponding catalyst prepared using deuterated ligand, (Ph-d₅)₂nacnac(H). ^a - indicates solvent used for NMR measurements. ^b - indicates solvent used for LR measurements. ^c - indicates solvent used for UV-VIS measurements.

Letter designations after the numbers in the LR results provide an indication of the strength of the designated peak: vs = very strong, s = strong, m = medium, and w = weak. 22

Table l.A-2 Interatomic Distances and Angles for (Ph)₂nacnacTiCl₂(THF)₂

(Note: the bond designations are with reference to FIG. 1 and the values noted in parentheses after the distances and angles represent the estimated standard deviation.)

Bond Distance (A) Bond Distance (A)

Ti-N(l) 2.086(3) C(4)-C(5) 1.366(6)

Ti-N(2) 2.088(3) C(5)-C(6) 1.392(5)

Ti-0(2) 2.209(3) C(7)-C(9) 1.386(5)

Ti-O(l) 2.213(3) C(7)-C(8) 1.513(5)

Ti-Cl(l) 2.3888(10) C(9)-C(10) 1.415(5)

Ti-Cl(2) 2.4001(10) C(10)-C(l l) 1.525(5)

N(l)-C(7) 1.336(4) C(12)-C(13) 1.378(6)

N(l)-C(l) 1.439(5) C(12)-C(17) 1.386(5)

N(2)-C(10) 1.325(4) C(13)-C(14) 1.395(6)

N(2)-C(12) 1.439(5) C(14)-C(15) 1.379(6)

0(1)-C(21) 1.440(6) C(15)-C(16) 1.354(7)

0(1)-C(18) 1.458(5) C(16)-C(17) 1.396(6)

0(2)-C(22) 1.428(6) C(18)-C(19) 1.470(7)

0(2)-C(25) 1.475(5) C(19)-C(20) 1.468(8)

C(l)-C(2) 1.378(5) C(20)-C(21) 1.514(8)

C(l)-C(6) 1.383(6) C(22)-C(23) 1.455(8)

C(2)-C(3) 1.392(6) C(23)-C(24) 1.463(9)

C(3)-C(4) 1.378(6) C(24)-C(25) 1.491(7)

Bond Angle Angle (deε.) Bond Angle Angle (deg.)

N(l)-Ti-N(2) 87.52(12) C(6)-C(l)-N(l) 1 19.9(3)

N(l)-Ti-0(2) 176.65(12) C(l )-C(2)-C(3) 120.8(4)

N(2)-Ti-0(2) 95.73(9) C(4)-C(3)-C(2) 1 19.4(4)

N(l)-Ti-0(1) 95.39(10) C(5)-C(4)-C(3) 120.3(4)

N(2)-Ti-0(1) 175.83(13) C(4)-C(5)-C(6) 120.4(4)

0(2)-Ti-0(l) 81.40(11) C(l)-C(6)-C(5) 120.0(4)

N(l)-Ti-Cl(l) 92.48(9) N(l )-C(7)-C(9) 123.9(3)

N(2)-Ti-Cl(l) 89.35(10) N(l)-C(7)-C(8) 120.6(3)

0(2)-Ti-Cl(l) 88.33(9) C(9)-C(7)-C(8) 1 15.5(3)

0(1)-Ti-Cl(l) 87.55(8) C(7)-C(9)-C(10) 127.9(3)

N(l)-Ti-Cl(2) 91.33(9) N(2)-C(10)-C(9) 124.1(3)

N(2)-Ti-Cl(2) 94.06(10) N(2)-C(10)-C(l l) 120.3(3)

0(2)-Ti-Cl(2) 87.69(9) C(9)-C(10)-C(l l) 1 15.6(3)

0(1)-Ti-Cl(2) 88.86(8) C(13)-C(12)-C(17) 119.4(3)

Cl(l)-Ti-Cl(2) 175.00(4) C(13)-C(12)-N(2) 119.7(3)

C(7)-N(l)-C(l) 117.1(3) C(17)-C(12)-N(2) 120.9(4)

C(7)-N(l)-Ti 127.4(2) C(12)-C(13)-C(14) 120.5(4)

C(l )-N(l)-Ti 1 15.3(2) C(15)-C(14)-C(13) 1 19.4(5)

C(10)-N(2)-C(12) 1 16.8(3) C(16)-C(15)-C(14) 120.5(4)

C(10)-N(2)-Ti 127.7(2) C(15)-C(16)-C(17) 120.7(4)

C(12)-N(2)-Ti 1 15.2(2) C(12)-C(17)-C(16) 119.6(4)

C(21)-0(l)-C(18) 106.5(3) 0(1)-C(18)-C(19) 107.4(4)

C(21)-0(1)-Ti 126.5(3) C(20)-C(19)-C(18) 108.0(4)

C(18)-0(1)-Ti 126.7(3) C(19)-C(20)-C(21) 104.9(5)

C(22)-0(2)-C(25) 107.1(3) O(l )-C(21)-C(20) 106.4(4)

C(22)-0(2)-Ti 127.4(3) 0(2)-C(22)-C(23) 108.2(5) 23

C(25)-0(2)-Ti 125.2(3) C(22)-C(23)-C(24) 107.1(5)

C(2)-C(l)-C(6) 1 19.1(3) C(23)-C(24)-C(25) 103.2(5)

C(2)-C(l )-N(l) 120.9(4) 0(2)-C(25)-C(24) 106.0(5)

Table 1A.3 Structure Determination Summary for

(Ph)₂nacnacTiCl₂(THF)₂

Crvstal Data

Formula C₂₅H33Cl₂N₂O₂Ti

Formula Weight 512.33

Crystal color red

Crystal Size (mm) 0.35 x 0.25 x 0.14

Crystal System orthorhombic

Space Group Pna2,

Unit Cell Dimensions a = 19.5601 (8)A b = 9.4959(4) A c = 13.5555(5) Λ = 90° β = 90° γ= 90°

Volume 2517.8(2) A³

Z 4

Density (calc.) 1.352 g/cm³

Absoφtion Coefficient 5.76 cm^"1

F(000) 1076

Data collection Diffractometer Used Siemens P4 Radiation MoKα (1 = 0.71073 A) Temperature 223(2) K Monochromator Highly oriented graphite crystal

2Θ Range (w) 4.16 to 56.66 Scan type Omega, Phi Scan Range 0.3° Index Ranges -18<h<20 -12 <k < 11 -18 < 1 < 17

Reflections Collected 9097 Independent Reflections 4584 (R_int = 3.41%) Observed Reflections 3916 24

Solution and Refinement

System Used SHELXTL (5.03) Solution Direct Methods

Refinement Method Full-Matrix Least-Squares Quantity minimized S[w(Fo² - F_c ²)²]/S[(wFo²)²] Hydrogen Atoms idealized contributions Weighting Scheme w^"1 = s²(F) + 0.0010 F² Final R Indices (obs. data) R = 4.15%, wR = 10.51% R Indices (all data) R = 5.34%, wR = 1 1.50% Goodness-of-Fit 1.272 Data-to-Parameter Ratio 15.8: 1 Largest Difference Peak 0.355 Largest Difference Hole -0.249

25

EXAMPLE IB

Preparation of 2,4-pentane di(N-phenyl)iminato dichloro bis- tetrahydrofuran vanadium, (Ph)₂nacnacVCl₂(THF)₂ and the

Corresponding Compound with the Deuterated Ligand, (Ph-</ )₂nacnac:

3.72 mmole (0.93g) of (Ph)₂nacnac(H) was dissolved in 50 ml of THF and cooled to -30°C in a round bottom flask. 3.72 mmoles MeLi solution was added slowly and allowed to stir for two hours to give a yellow solution of

(Ph)₂nacnacLi in THF with gas evolution. After the reaction mixture was allowed to stir until no more bubbles were observed, it was cooled to -30°C. In a separate round bottom flask, 3.72 mmoles (1.37 g) of VC1₃(THF)₃ was dissolved in 150 ml of THF. The THF solution of (Ph)₂nacnacLi was then transferred to an addition funnel and added dropwise to the THF solution of

VC1₃(THF)₃ over a three hour period. The color of the solution slowly changed from dark red to puφle brown and finally dark green. After stirring overnight, the solvent was evaporated to dryness. The resulting brown solid, was extracted with toluene, by trituration in ether. The brown solution was then filtered and toluene was vacuum removed. The solid was dissolved in

THF which turned dark green. The THF solution was cooled to -30°C for crystallization. Dark green microcrystalline powder was isolated by filtration and washed with cold THF several times. After drying under vacuum, 1.05 g (55 % yield) of (Ph)₂nacnacVCl₂(THF)₂ was isolated.

The resulting compounds were analytically tested and the results are shown in Tables IB.1-3. The single crystal X-ray diffraction results are shown in Fig. 2. 26

TABLE 1B.1

ANALYTICAL DATA FOR

(Ph)₂nacnacVCl₂(THF)₂ (Ph- ₅)2nacnacVCl₂(THF)2

'HNMR(CD₂Cl₂)^a: 111.52 99.81 86.72 25-8 8.49 5.55 1.83 δ (ppm) (2H,b) (2H,b) (lH,b) (4H,vb) (1H) (HH,b) (8H)

'HNMR(THF-d₈)^a: 107.59 86.92 12.22 6.23 *** *** *** δ (ppm) (6H) (1H) (4H) (6H)

'HNMR(THF-d₈)^a: 108.76 85.80 *** *** *** t (6H) (1H) δ (ppm) HNMR(THF)^a: 12.1 6.2 *** *** *** *** *** δ (ppm) (4D) (6D)

IR - KBr^b: (cm¹) 3053m 3031m 2968s 2927m 2879m 1590m 1532s

1485s 1435m 1430m 1368m 1319s 1066w 1021s

924s 920m 875s 844s 784w 779m 708s 524w

IR - KBr^b; (cm¹): * 2968m 2927m 2876m 2269w 1561m 1528vs 1430m

1382vs 1318vs 1242m 1021s 924w 870m 854m

81 l 779w 556m 457m *** *** ***

Mass Spectrometry: 369.99 (37) [M⁺ - (THF)₂] 299.04 (32) [M⁺ - C1(THF)₂] m/z (%)

Mass Spectrometry: 380.02 (100.0) [M⁺ - (THF)₂] 345.05 (2.54) [M⁺ - C1(THF)₂] t m/z (%)

UV-vis(THF)⁰: 598(1,318.4 M^cm^"1) 474(1,404.2 M'cm^"1) 350(10,57 λmax(ε) 4.7 M^" 'cm') μ.ff 3.2(std. dev.1), μ_B (294K)

Melting Pt. Range: 162 - 164°C

C₂₅H₃₃N₂0₂VC1₂ , • 1

Calculated: C 58.26 H6.45 N5.44 ( )

Measured: (%) C 57.81 H6.37 N3.77

27

Table 1B.2 Interatomic Distances and Angles for (Ph)₂nacnacVCl₂(THF)₂

(Note the bond designations are with reference to FIG 2 and the values noted in parentheses after the distances and angles represent the estimated standard deviation )

Bond Distance (A) Bond Distance (A)

V(l)-N(l) 2023(2) C(6)-C(ll) 1382(4)

V(l)-N(2) 2030(2) C(7)-C(8) 1379(5)

V(l)-0(1) 2208(2) C(8)-C(9) 1366(5)

V(l)-0(2) 2221(2) C(9)-C(10) 1393(4)

V(1)-C1(1) 23592(6) C(10)-C(ll) 1389(3)

V(1)-C1(2) 23646(6) C(12)-C(13) 1383(4)

0(1)-C(21) 1445(4) C(12)-C(17) 1385(4)

0(1)-C(18) 1456(4) C(13)-C(14) 1397(4)

0(2)-C(25) 1447(4) C(14)-C(15) 1382(4)

0(2)-C(22) 1480(4) C(15)-C(16) 1386(4)

N(l)-C(l) 1345(3) C(16)-C(17) 1393(4)

N(l)-C(ll) 1430(3) C(18)-C(19) 1506(5)

N(2)-C(3) 1337(3) C(19)-C(20) 1471(6)

N(2)-C(17) 1431(3) C(20)-C(21) 1488(5)

C(l)-C(2) 1400(3) C(22)-C(23) 1518(5)

C(l)-C(4) 1523(4) C(23)-C(24') 139(2)

C(2)-C(3) 1395(4) C(23)-C(24) 1559(13)

C(3)-C(5) 1509(3) C(24)-C(25) 1383(10)

C(6)-C(7) 1380(4) C(24')-C(25) 1597(12)

Bond Angle Angle (de Bond Angle Angle (deg )

N(l)-V(l)-N(2) 9094(9) N(2)-C(3)-C(2) 1235(2)

N(l)-V(l)-0(2) 9415(7) N(2)-C(3)-C(5) 1206(2)

N(2)-V(l)-0(2) 17489(9) C(2)-C(3)-C(5) 1158(2)

N(l)-V(l)-0(1) 17475(9) C(7)-C(6)-C(ll) 1209(3)

N(2)-V(l)-0(1) 9345(7) C(8)-C(7)-C(6) 1200(3)

0(2)-V(l)-0(l) 8144(8) C(9)-C(8)-C(7) 1198(3)

N(1)-V(1)-C1(1) 8968(7) C(8)-C(9)-C(10) 1207(3)

N(2)-V(1)-C1(1) 9135(7) C(ll)-C(10)-C(9) 1197(3)

0(2)-V(l)-Cl(l) 8824(7) C(6)-C(ll)-C(10) 1189(3)

0(1)-V(1)-C1(1) 8733(6) C(6)-C(ll)-N(l) 1202(2)

N(1)-V(1)-C1(2) 9378(7) C(10)-C(ll)-N(l) 1208(2)

N(2)-V(1)-C1(2) 9222(7) C(13)-C(12)-C(17) 1210(3)

0(2)-V(l)-Cl(2) 8790(7) C(12)-C(13)-C(14) 1196(3)

0(1)-V(1)-C1(2) 8893(6) C(15)-C(14)-C(13) 1198(3)

C1(1)-V(1)-C1(2) 17499(3) C(14)-C(15)-C(16) 1202(3)

C(21)-0(l)-C(18) 1065(2) C(15)-C(16)-C(17) 1204(3)

C(21)-0(1)-V(l) 1268(2) C(12)-C(17)-C(16) 1190(3)

C(18)-0(1)-V(l) 1258(2) C(12)-C(17)-N(2) 1203(2)

C(25)-0(2)-C(22) 1082(3) C(16)-C(17)-N(2) 1207(2)

C(25)-0(2)-V(l) 1265(2) 0(1)-C(18)-C(19) 1059(3)

C(22)-0(2)-V(l) 1250(2) C(20)-C(19)-C(18) 1060(3)

C(l)-N(l)-C(ll) 1164(2) C(19)-C(20)-C(21) 1070(3)

C(l)-N(l)-V(l) 1262(2) O(l)-C(21)-C(20) 1072(3)

C(ll)-N(l)-V(l) 1171(2) 0(2)-C(22)-C(23) 1048(3)

C(3)-N(2)-C(17) 1176(2) C(24')-C(23)-C(22) 1020(7)

C(3)-N(2)-V(l) 1258(2) C(22) C(23)-C(24) 1055(5)

C(17)-N(2)-V(l) 1164(2) C(25)-C(24)-C(23) 1069(7)

N(l)-C(l)-C(2) 1233(2) C(23)-C(24')-C(25) 1047(6)

N(l)-C(l)-C(4) 1203(2) C(24)-C(25)-0(2) 1107(5)

C(2)-C(l)-C(4) 1164(2) 0(2) C(25)-C(24') 1023(7)

C(3)-C(2)-C(l) 1288(2) 28

Table 1B.3 Structure Determination Summary for (Ph)₂nacnacVCl₂(THF)₂

Crystal Data Formula C₂₅H33CI2N₂O₂V Formula weight 515.37 Crystal color black block Crystal Size (mm) 0.35 x 0.25 x 0.14 Crystal System orthorhombic Space Group Pna2, Unit Cell Dimensions a = 19.5215(4) A b = 9.5341(2) A c = 13.4898(3) A = 90° β = 90° γ = 90°

Volume 2510.72(9) A³

Z 4

Density (calc.) 1.363 g/cm³

Absoφtion Coefficient 6.32 cm^"1

F(000) 1080

Data collection Diffractometer Siemens P4 Radiation MoKα (1 = 0.71073 A)

Temperature 218(2) K Monochromator Highly oriented graphite crystal

20 Range (w) 4.18 to 56.56° Scan type Omega, Phi

Scan Range 0.3° Index Ranges -25 <h < 12 -10<k<12 -17 < 1 < 17 Reflections Collected 9021

Independent Reflections 5585 (R_ιnt = 2.04%) Observed Reflections 4948 29

Solution and Refinement

System Used SHELXTL (5.03) Solution Direct Methods

Refinement Method Full-Matrix Least-Squares Quantity minimized S[w(Fo² - F_c ²)²]/S[(wF₀ ²)²]^1/2 Hydrogen Atoms Idealized contributions Weighting Scheme w^"1 = s²(F) + 0.0010 F² Final R Indices (obs. data) R = 3.75%, wR = 8.23% R Indices (all data) R = 4.67%, wR = 9.77% Goodness-of-Fit 1.390 Data-to-Parameter Ratio 18.6: 1 Largest Difference Peak 0.301 Largest Difference Hole -0.240

30

EXAMPLE IC

Preparation of 2,4-pentane di(N-phenyl)iminato dichloro bis- tetrahydrofuran chromium, (Ph)₂nacnacCrCI₂(THF)₂ and the

Corresponding Compound with the Deuterated Ligand, (Ph-rf )₂nacnac:

2.40 mmole (0.6 g,) of (Ph)₂nacnacH was dissolved in 50 ml of THF and cooled to -30°C. 2.40 mmoles (53 mg) of MeLi was slowly added as a solid with stirring. The THF solution of (Ph)₂nacnacLi prepared in-situ was then slowly added over a three hour period to a slurry of 2.40 mmoles (900 mg,) of CrCl₃(THF)₃ in 150 ml of THF. The color of the solution changed from a purple to red brown. After stirring at room temperature overnight, the reaction mixture was concentrated to 50 ml and cooled to -30°C for crystallization. A brown microcrystalline powder was isolated by filtration. After washing with cold THF several times and drying under vacuum, 2.09 mmoles (1.08 g, 87% yield) of the resulting (Ph)₂nacnacCrCl₂(THF)2 compound was isolated.

The resulting compounds were analytically tested and the results are shown in Tables 1C.1-3. The single crystal X-ray diffraction results are shown in Fig. 3.

31

TABLE lC.l ANALYTICAL DATA FOR

(Ph)₂nacnacCrCl₂(THF)₂ (Ph-J₅)₂nacnacCrCl₂(THF)₂

Η NMR (CD₂Cl₂)^a: 111.52 99.81 86.72 25-8 8.49 5.55 1.83 δ (ppm) (2H,b) (2H,b) (lH,b) (4H,vb) (1H) (HH,b) (8H)

'HNMR(THF-d₈)^a: 15.46 6.19 12.22 6.23 *** #*# **# δ (ppm) (6H) (4H) (4H) (6H)

Η NMR (THF) ^a: 16.1 15.4 6.1 *** *** t (4D) (2D) (4D) δ (ppm)

IR-KBr^b:(cm^"'): 3050w 3017m 2966s 2928s 2883s 1590w 1555vs

1530vs 1484vs 1448vs 1387vs 1263s 1200s 1065 1017s w

921m 871m 848s 764m 710s 662 526m 477w

IR-KBr^b:(cm'): 2967m 2926m 2878m 2269w 1550m 1528vs 1453m t

1381vs 1320vs 1157m 1016m 969m 869m 855m

811w 753m 558m 427m *** *** ***

UV-vis(THF)^c: 598(1,318.4 M'cm^"1) 474(1,404.2 M^"W) 350(10,574.7 M'cm^"1) λmax(ε)

Mass Spectrometry: 370.76(41.24) 335.81(41.60) 300.86(6.01) m/z (%) [M⁺-(THF)₂] [M⁺ - C1(THF)₂] [M⁺-C1₂(THF)₂]

Mass Spectrometry: 381.02(19.41) 346.05(46.83) 311.09(5.45) ⁺ m/z (%) [M⁺ - (THF)₂] [M⁺ - C1(THF)₂] [M⁺-C1₂(THF)₂]

UV-vis(THF)^c: 527(572.2 M^"'cm^'') 419(8,232.5 M'cm^"1) 400(5,711.7 M'cm^"1) λma (ε) μ«ff 4.1(std. dev.1), μ_B (294K)

Melting Pt. Range: 174- 180°C

C₂,H₃₃N₂0₂CrCl₂

Calculated: C58.14 H6.44 N5.42

(%)

Measured: (%) C 57.95 H6.81 N5.51

32

Table 1C.2 Interatomic Distances and Angles for (Ph)₂nacnacCrCl₂(THF)

(Note the bond designations are with reference to FIG 3 and the values noted in parentheses after the distances and angles represent the estimated standard deviation )

Bond Distance (A) Bond Distance (A)

Cr(l)-N(l) 2032(6) C(6)-C(7) 1398(7)

Cr(l)-N(2) 2033(5) C(7)-C(8) 1415(8)

Cr(l)-0(2) 2141(5) C(8)-C(9) 1347(9)

Crd)-O(l) 2144(5) C(9)-C(10) 1402(8)

Cr(l)-Cl(l) 23392(12) C(10)-C(ll) 1415(7)

Cr(l)-Cl(2) 23532(12) C(12)-C(17) 1369(7)

0(1)-C(18) 1462(8) C(12)-C(13) 1406(8)

0(1)-C(21) 1464(8) C(13)-C(14) 1383(8)

0(2)-C(25) 1459(8) C(14)-C(15) 1393(8)

0(2)-C(22) 1473(8) C(15)-C(16) 1374(8)

N(l)-C(l) 1315(8) C(16)-C(17) 1424(7)

N(l)-C(ll) 1459(7) C(18)-C(19) 1526(9)

N(2)-C(3) 1323(8) C(19)-C(20) 1519(11)

N(2)-C(17) 1453(7) C(20)-C(21) 1492(10)

C(l)-C(2) 1431(7) C(22)-C(23) 1497(10)

C(l)-C(4) 1537(8) C(23)-C(24') 140(3)

C(2)-C(3) 1412(8) C(23)-C(24) 158(2)

C(3)-C(5) 1525(8) C(24)-C(25) 147(2)

C(6)-C(ll) 1377(8) C(24')-C(25) 150(3)

Bond Angle Angle (deg ) Bond Angle Angle (deg )

N(l)-Cr(l)-N(2) 917(2) N(2)-C(3)-C(2) 1247(5)

N(l)-Cr(l)-0(2) 934(2) N(2)-C(3)-C(5) 1212(6)

N(2)-Cr(l)-0(2) 1748(2) C(2)-C(3)-C(5) 1141(6)

N(l)-Cr(l)-0(1) 1760(2) C(ll)-C(6)-C(7) 1217(5)

N(2)-Cr(l)-0(1) 921(2) C(6)-C(7)-C(8) 1180(5)

0(2)-Cr(l)-0(l) 827(2) C(9)-C(8)-C(7) 1205(6)

N(l)-Cr(l)-Cl(l) 885(2) C(8)-C(9)-C(10) 1222(6)

N(2)-Cr(l)-Cl(l) 895(2) C(9)-C(10)-C(ll) 1180(6)

0(2)-Cr(l)-Cl(l) 901(2) C(6)-C(ll)-C(10) 1196(5)

0(1)-Cr(l)-Cl(l) 9028(13) C(6)-C(ll)-N(l) 1211(5)

N(l)-Cr(l)-Cl(2) 906(2) C(10)-C(ll)-N(l) 1191(5)

N(2)-Cr(l)-Cl(2) 901(2) C(17)-C(12)-C(13) 1208(5)

0(2)-Cr(l)-Cl(2) 903(2) C(14)-C(13)-C(12) 1198(5)

0(1)-Cr(l)-Cl(2) 9071(13) C(13)-C(14)-C(15) 1195(6)

Cl(l)-Cr(l)-Cl(2) 17895(11) C(16)-C(15)-C(14) 1213(5)

C(18)-0(l)-C(21) 1063(6) C(15)-C(16)-C(17) 1193(5)

C(18)-0(1)-Cr(l) 1265(4) C(12)-C(17)-C(16) 1193(5)

C(21)-0(1)-Cr(l) 1258(4) C(12)-C(17)-N(2) 1216(5)

C(25)-0(2)-C(22) 1074(6) C(16)-C(17)-N(2) 1190(5)

C(25)-0(2)-Cr(l) 1269(4) 0(1)-C(18)-C(19) 1059(6)

C(22)-0(2)-Cr(l) 1252(5) C(20)-C(19)-C(18) 1038(6)

C(l)-N(l)-C(ll) 1171(5) C(21)-C(20)-C(19) 1074(6)

C(l)-N(l)-Cr(l) 1257(4) O(l)-C(21)-C(20) 1068(6)

C(ll)-N(l)-Cr(l) 1168(4) 0(2)-C(22)-C(23) 1058(7)

C(3)-N(2)-C(17) 1177(5) C(24')-C(23)-C(22) 1004(12)

C(3)-N(2)-Cr(l) 1253(4) C(22)-C(23)-C(24) 1094(9)

C(17)-N(2)-Cr(l) 1170(4) C(25)-C(24)-C(23) 1013(13)

N(l)-C(l)-C(2) 1246(6) C(23)-C(24')-C(25) 109(2)

N(l)-C(l)-C(4) 1212(5) C(24)-C(25)-0(2) 1123(10)

C(2)-C(l)-C(4) 1142(6) 0(2)-C(25)-C(24') 103(2)

C(3)-C(2)-C(l) 1269(6) 33

Table 1C.3 Structure Determination Summary for (Ph)₂nacnacCrCl₂(THF)

Crystal Data Empirical Formula C₂₅H₃3Cl₂N₂O₂Cr Color; Habit brown plate Crystal Size (mm) 0.35 x 0.35 x 0.12 Crystal System orthorhombic Space Group Pna2, Unit Cell Dimensions a = 19.6220(4) A b = 9.5971(2) A c = 13.4509(3) A α = 90° β = 90° γ= 90°

Volume 2533.00(9) A³

Z 4

Formula Weight 516.43

Density (calc.) 1.354 g/cm³

Absorption Coefficient 6.87 cm^"1

F(000) 1084

Data collection Diffractometer Used Siemens P4/CCD Radiation MoKα (1 = 0.71073 A)

Temperature 218(2) K Monochromator Highly oriented graphite crystal

2Θ Range (w) 4.16 to 56.12° Scan type Omega, Phi

Scan With 0.3° Index Ranges -24 <h < 25 -12 < k < 12 -16 < 1 < 13 Reflections Collected 9160

Independent Reflections 4228 (R_int = 13.02%) Observed Reflections 2408 34

Solution and Refinement

System Used SHELXTL (5.03) Solution Direct Methods

Refinement Method Full-Matrix Least-Squares Quantity minimized S[w(F₀ ² - F_c ²)²]/S[(wF₀ ²)²]^1/2 Hydrogen Atoms Idealized contributions Weighting Scheme w^"' = s²(F) + 0.0010 F² Final R Indices (obs. data) R = 5.35%, wR = 11.14% R Indices (all data) R =10.56%, wR = 16.45% Goodness-of-Fit 0.808 Data-to-Parameter Ratio 14.2: 1 Largest Difference Peak 0.375 Largest Difference Hole -0.880

EXAMPLE 2A

Preparation of 2,4-pentane di(N-phenyI)iminato chloro methyl vanadium, (Ph)₂nacnacV(Cl)(Me):

0.97 mmoles (0.500 g) of (Ph)₂nacnacVCl₂(THF)₂, reference Example IB, was dissolved in 150 ml of THF and the solution was cooled to -30°C. 0.97 mmoles of MeLi in ether was slowly added to the suspension of (Ph)₂nacnacVCl2(THF)2 in THF which caused a color change from dark green to dark red brown. After stirring for 5 hours, the reaction mixture was evaporated to dryness. The residual THF was removed by trituration in ether. The brown solid was then extracted with ether and filtered to remove LiCl. The ether solution was concentrated and cooled to -30°C for crystallization. A microcrystalline brown powder was filtered and washed with cold pentane. After drying under vacuum, 0.202 g (59 % yield) of (Ph)₂nacnacV(Cl)(Me) was isolated. The resulting compound was analytically tested and the results are shown in Table 2A. 35

TABLE 2A

ANALYTICAL DATA FOR (Ph)₂nacnacV(Cl)(Me)

'HNMR(C₆D₆)^a: 8.70 -3.90 *** **# *** *** *** δ (ppm) (6H,vb) (2H,vb)

IR-KBr^b:(cm') 3057w 3029w 2992w 2959w 2918w 2848w 1592m

1530s 1510m 1483s 1447m 1427m 1371s 1339s

1299m 1262m 1184w 1071w 1023m 1023s 997m

937w 918w 854w 799w 754s 700s 515m

Mass Spectrometry: 350(15) 335(100) 299(6) m/z (%) [M⁺] [M⁺ - CH,] [M⁺ - CH,CL]

UV-vis(Et₂0)^c: 541 (4.27xl0⁴M^"'cm') 435(1.42xl0ⁱM^"1cm-¹)

^ma (E)

Meff 3.0(std. dev.1), μ_B (294K)

Melting Pt. Range: 132- 134°C

C₁₈H₂₀N₂VC1

Calculated: C 61.64 H5.75 N7.99

(%)

Measured: (%) C 61.53 H5.74 N7.98

36

EXAMPLE 2B

Preparation of 2,4-pentane di(N-phenyl)iminato chloro trimethylsilylmethyl vanadium, (Ph)₂nacnacV(Cl)(CH₂Si(CH₃)₃):

0.58 mmoles (300 mg) of (Ph)₂nacnacVCl₂(THF)₂, reference Example IB, was dissolved in 50 ml of diethylether and the solution was cooled to -30°C. 0.58 mmoles of LiCH₂Si(CH₃)₃) in a diethylether solution was added slowly to the (Ph)₂nacnacVCl₂(THF)2 in diethylether solution which clouded the brown solution without an observable color change. After stirring overnight at room temperature, the reaction mixture was evaporated to dryness. The dark brown oil was dissolved in pentane and evaporated to dryness twice to remove residual THF. The solid was then extracted with pentane and filtered to remove LiCl. The solvent was again evaporated and the dark red brown oil was dissolved in a minimum amount of HMDS with some drops of pentane and cooled to -30°C for crystallization. 124 mg (505 yield) of dark brown (Ph)₂nacnacV(Cl)(CH₂Si(CH₃)₃ crystals were isolated after two crystallization extraction cycles. The crystals were analytically tested and the results are shown in Table 2B.

37

TABLE 2B

ANALYTICAL DATA FOR (Ph)₂nacnacV(Cl)(CH₂Si(CH₃)₃) ^lH NMR (C₆D₆) ^a: 8.69 -1.40 3.16 *** *#* *** *** δ (ppm) (6H) (9H) (2H)

IR - KBr^b: (cm ') 3056w 3026w 2999w 2956m 2922m 2850w 1593m

1532s 1510m 1485s 1447m 1431m 1371vs 1299m 1251m

1071 w 1022m 998m 848s 757m 701s 488w 471w

Mass Spectrometry: 422(7) [M⁺] 335(57) [M⁺ - CH₂Si(CH₃)₃] m/z (%)

UV-vis (Et₂0) ^c: 541 (266 M ' cm^"') 629 (421 M^"' cm^"1) λma (ε)

Heff 3.0(std. dev. 1), μ_B (294K)

Melting Pt. Range: 250-254°C

C₂₁H₂₈N₂ClVSi

Calculated: C 59.70 H 6.69 N 6.63

( )

Measured: (%) C 59.59 H 6.58 N 6.39

EXAMPLE 3A

Preparation of 2,4-pentane di(N-phenyI)iminato dimethyl vanadium,

(Ph)₂nacnac VMe₂ :

5.0 mmoles (2.58g,) of (Ph)₂nacnacVCl₂(THF)₂, reference Example IB, was suspended in 150ml of THF and cooled to -30°. 1 1.0 mmoles (2.2 equiv.) of MeLi was added slowly causing a color change from dark green to dark brown. After stirring for 5 hours, the reaction mixture was evaporated to dryness. The brown solid was dissolved in diethylether and evaporated to dryness twice to remove residual THF. The solid was then extracted with diethlyether and filtered to remove LiCl. The solution was concentrated to 30 ml of ether and cooled to -30°C for crystallization. 1.397 g of brown cubic

(Ph)₂nacnacVMe₂ crystals containing chloride impurity of (Ph)₂nacnacV(Cl)(Me) were isolated after vacuum drying. The content of the chloride impurity ranges from 18 to 50%. 38

The resulting compounds were analytically tested and the results are shown in Tables 3A.1-3. The single crystal X-ray diffraction results are shown in Fig.4.

TABLE 3A.1

ANALYTICAL DATA FOR

(Ph)₂nacnacVMe₂

'HNMR(C₆D₆)^a: 8.68 -4.99 *** *** *** *** *** δ (ppm) (6H) (2H)

IR-KBr:(cm') 3053m 3031m 2968s 2927m 2879m 1590m 1532s

1485s 1435m 1430m 1368m 1319s 1066w 1021s

924w 920m 875s 844s 784w 779m 708s 524w

Mass Spectrometry: 330 (23.4) 315(22.29) 300(29.24) m/z (%) [M⁺] [M⁺ - CH,] [M⁺ - 2CH,]

UV-vis(Et₂OV: 597 (194.4 M'cm^"') 446 (334 M^"1 cm^"') λm x(ε)

Hcff 3.1(std. dev.1), μ„ (294K)

Melting Pt. Range: 125-129°C

C,αH₂,N₂V

Calculated: (%) C 69.08 H7.02 N8.48

Measured: (%) C 64.76 H6.36 N8.29

39

Table 3A.2 Interatomic Distances and Angles for (Ph)₂nacnacVMe₂

(Note: the bond designations are with reference to FIG. 4 and the values noted in parentheses after the distances and angles represent the estimated standard deviation )

Bond Distance (A) Bond Distance (A)

V-N(l ) 1.963(3) C(7)-C(8) 1.398(5)

V-N(2) 1.972(3) C(7)-C(12) 1.415(6)

V-C(l ) 2.080(4) C(8)-C(9) 1.387(6)

V-C 2.126(4) C(9)-C(10) 1.385(7)

N(l)-C(2) 1.353(5) C(10)-C(l l) 1.396(6)

N(l )-C(12) 1.448(5) C(l l)-C(12) 1.378(6)

N(2)-C(4) 1.335(5) C(13)-C(18) 1.388(6)

N(2)-C(18) 1.433(5) C(13)-C(14) 1.409(6)

C(2)-C(3) 1.405(5) C(14)-C(15) 1.377(7)

C(2)-C(5) 1.523(5) C(15)-C(16) 1.382(7)

C(3)-C(4) 1.416(5) C(16)-C(17) 1.388(6)

C(4)-C(6) 1.531(5) C(17)-C(18) 1.383(6)

Bond Angle Angle (deg.) Bond Angle Angle (deg.)

N(l)-V-N(2) 92.1 1(13) C(3)-C(4)-C(6) 1 17.6(3)

N(l)-V-C(l) 1 1 1.1(2) C(8)-C(7)-C(12) 120.0(4)

N(2)-V-C(l) 1 15.1(2) C(9)-C(8)-C(7) 120.4(4)

N(l )-V-C 1 14.72(14) C(10)-C(9)-C(8) 119.4(4)

N(2)-V-C 108.4(2) C(9)-C(10)-C(l l) 120.5(4)

C(l)-V-C 113.6(2) C(12)-C(l l)-C(10) 120.9(4)

C(2)-N(l)-C(12) 120.4(3) C(l l)-C(12)-C(7) 1 18.6(4)

C(2)-N(l)-V 127.6(3) C(l l)-C(12)-N(l) 123.5(4)

C(12)-N(l)-V 1 1 1.8(2) C(7)-C(12)-N(l) 1 17.6(3)

C(4)-N(2)-C(18) 119.2(3) C(18)-C(13)-C(14) 1 19.6(4)

C(4)-N(2)-V 127.2(3) C(15)-C(14)-C(13) 1 19.7(4)

C(18)-N(2)-V 1 13.5(2) C(14)-C(15)-C(16) 120.3(4)

N(l)-C(2)-C(3) 122.0(3) C(15)-C(16)-C(17) 120.4(5)

N(l )-C(2)-C(5) 120.9(3) C(18)-C(17)-C(16) 1 19.9(4)

C(3)-C(2)-C(5) 1 17.1(3) C(17)-C(18)-C(13) 120.1 (4)

C(2)-C(3)-C(4) 127.8(4) C(17)-C(18)-N(2) 120.2(4)

N(2)-C(4)-C(3) 122.9(3)

C(13)-C(18)-N(2) 119.5(4)

N(2)-C(4)-C(6) 1 19.4(3)

40

Table 3A.3 Structure Determination Summary for (Ph)₂nacnacVMe₂

Crystal Data Formula C₁₉H₂₃N₂V Formula weight 330.13 Crystal color brown block Crystal Size (mm) 0.40 x 0.20 x 0.10 Crystal System monoclinic Space Group P2Jn Unit Cell Dimensions a = 8.6616(2) A b = 15.9937(4) A c = 13.2812(1) A α = 90° β = 93.317(2)° γ= 90°

Volume 1836.78(8) A³

Z 4

Density (calc.) 1.220 g/cm³

Absorption Coefficient 6.05 cm^"1

F(000) 712

Data collection Diffractometer Siemens P4 Radiation MoKα (1 = 0.71073 A) Temperature 295(2) K Monochromator Highly oriented graphite crystal

2Θ Range (w) 3.98 to 56.30° Scan type Omega, Phi Scan Range 0.3° Index Ranges -1 1 <h < 10 18 < k < 21 -17 < 1 < 16

Reflections Collected 7272 Independent Reflections 3894 (R_int = 4.00%) Observed Reflections 41

Solution and Refinement

System Used Siemens SHELXTL (5.03) Solution Direct Methods

Refinement Method Full-Matrix Least-Squares Quantity minimized S[w(F₀ ² - F_c ²)²]/S[(wFo²)²]^{I 2} Hydrogen Atoms Idealized contributions Weighting Scheme w^"1 = s²(F) + 0.0010 F² Final R Indices (obs. data) R =6.01%, wR = 15.52% R Indices (all data) R = 10.22%, wR = 19.76% Goodness-of-Fit 1.167 Data-to-Parameter Ratio 19.37: 1 Largest Difference Peak 0.488 Largest Difference Hole -0.492

42

EXAMPLE 3B

Preparation of 2,4-pentane di(N-phenyl)iminato u^'s-trimethyl silylmethyl vanadium, (Ph)2nacnacV(CH₂Si(CH₃)3)2:

1.94 mmoles (1.00 g) of (Ph)₂nacnacVCl2(THF)₂, reference Example IB, was dissolved in 150 ml of THF and the solution was cooled to -30°C. 3.88 moles (0.366 g) of LiCH₂Si(CH₃)₃ crystals were slowly added to the THF solution which caused a color change from dark green to dark red brown.

After stirring at room temperature for 4 hours, the reaction mixture was evaporated to dryness. By trituration in pentane, the residual THF was removed. A dark brown solid was extracted with pentane and filtered to remove LiCl. After the solvent was removed from the filtrate, the resulting brown oil was dissolved in HMDS and cooled to -30°C. No solid was isolated. However, 0.11 g (65 % yield) of a dark brown oil, i.e., (Ph)₂nacnacV(CH₂Si(CH₃)₃)₂, was isolated by evaporation of the solvent. The oil was analyzed and the results are shown in Table 3B.

TABLE 3B ANALYTICAL DATA FOR (Ph)2nacnacV(CH₂Si(CH₃)₃)2

'H NMR (C₆D₆) ^a: 8.56 -0.92 -3.69 *** *** *** *** δ (ppm) (6H) (18H) (2H)

IR - neat^b: (cm^"1): 306 lw 303 lw 2948s 2889m 2862w 2816w 1592m

, _' 1528s 1510s 1483vs 1447s 1429m 1362vs 1262m 1241s

1184w 1069w 1025m 935w 884vs 845vs 750s 700vs

Mass Spectrometry: m/z 474.32(4.1) [M⁺] 386.22(58.47) 300(24.56)

(%) [M⁺ - SiMe₄] [M⁺ - 2CH₂Si(CH₃)₃]

43

EXAMPLE 4

Preparation of 2,4-pentane di(N-phenyl)iminato (OTf)₂ bis- tetrahydrofuran vanadium, (Ph)₂nacnacV(OTf)2(THF)₂

0.52 mmoles (270 mg,)(Ph)₂nacnacVCl₂(THF)₂, reference Example IB, were dissolved in 40 ml of THF. 1.04 mmoles (280 mg) of AgOTf was added as a solid to the THF solution. After stirring overnight, the solution was filtered to remove AgCl. The dark green solution was concentrated and cooled to -30°C for crystallization. 340 mg (87% yield) of dark green (Ph)₂nacnacV(OTf)₂(THF)₂ crystals were isolated. The crystals were analyzed and the results are shown in Table 4.

TABLE4 ANALYTICALDATA FOR

(Ph) ₂nacnac V ( Tf)₂( TH F

'H NMR (THF-d₈) ^a. 126.94 15.91 3.28 *** *** **# *** δ (ppm) (6h,vb) (4H,vb) (4H)

IR - KBr^b: (cm ¹) 306 lw 303 lw 2985w 2933w 2907w 1592w 1540m

1487s 1447w 1434w 1339vs 1236vs 1201 vs 1014s

928w 850m 844s 764w 710m 632s 524w

Mass Spectrometry: 597.98(64) [M⁺ - 2THF] 465.02(54.3) m/z (%) [M⁺ - S0₂CF,,2THF]

UV-vιs (THF) ^c 598(1,318.4 M 'cm ') 474(1 ,404.2 M 'cm ¹) 350(10,574 7 M 'cm ') λma (ε) μ.ff 3.2(std. dev l), μ_B (294K)

Melting Pt. Range: 160 - 163°C

C₂₇H₃₁N₂0₈F₆S₂V

Calculated: C 43.66 H 4.48 N 3.77 ^: (%)

Measured' (%) C 42.53 H4.59 N3.87

44

EXAMPLE 5A

Preparation of 2,4-pentane di(N-phenyl)iminato methyl diethylether tetrahydrofuran vanadium tetrαA; 5-(3,5-6 s-trifluoromethyl- phenyl)borate, [(Ph)₂nacnacVMe(Et₂O)(THF)][B(C₆H₃(CF₃)2)₄]:

0.30 mmoles (100 mg) (Ph)₂nacnacVMe₂, reference Example 3 A, was dissolved in 20 ml of diethylether and cooled to -30°C. In a separate flask, .30 mmoles (310 mg) of H(Et₂O)₂[B(C₆H₃(CF₃)₂)₄] was dissolved in 10 ml of diethylether and cooled to -30.C. The diethylether solution of H(Et₂O)₂[B(C₆H₃(CF₃)₂)₄] was slowly added by pipette to the cold solution of (Ph)₂nacnacVMe₂. With gas evolution, the color of the solution turned to slightly darker brown. 0.21 mmoles (278 mg, 69 % yield) of orange t(Ph)2nacnacVMe(Et₂O)(THF)][B(C₆H3(CF3)2)₄] crystals were isolated from a concentrated diethylether solution containing a several drops of THF that was cooled to -30°C.

The resulting compounds were analytically tested and the results are shown in Tables 5A.1-3. The single crystal X-ray diffraction results are shown in Fig. 5.

TABLE 5A.1

ANALYTICAL DATA FOR r(Ph)₂nacnacVMe(Et₂O)(THF)][B(C₆H₃(CF₃)₂)₄]

'H NMR (CD₂Cl₂) ^a: 121.4 90.5 8.68 7.73 7.57 0.90 -2.46 δ (ppm) (6H,vb) (lH.vb) (4H,vb) (8H) (4H) (8H,b) (2H,vb)

IR - KBr^b: (cm^"') 3087w 2982w 2936w 2907w 1610w 1555m 1486m

1450w 1429w 1356vs 1284vs 1 158vs,b 1133vs,b 1020m

938s 897s 795w 758w 710s 700s 679s

670s 525w 496w *** *** *** ***

UV-vis (Et₂0) ^c: 739(222 M 'cm^"1) 609(334 M^{' 1}) 475(1350 M ) λ_ma fø)

H ff 3.4(std. dev. 1), μ„ (294K)

Melting Pt. Range: 95-97°C

C_JH_UN_.O_IF_MVB

Calculated: (%) C 53.02 H 3.84 N 2.13

Measured: (%) C 49.89 H 3.28 N 2.16 45

Table 5A.2 Interatomic Distances and Angles for the Cation of

[(Ph)2nacnacVMe(Et₂O)(THF)][B(C₆H₃(CF₃)2)₄]

(Note: the bond designations are with reference to FIG. 5 and the values noted in parentheses after the distances and angles represent the estimated standard deviation.)

Bond Distance (A) Bond Distance (A)

V-N(2) 1.94(2) C(8)-C(9) 1.39(4)

V-N(l) 2.00(2) C(10)-C(l l) 1.38(3)

V-O(l) 2.029(13) C(10)-C(14) 1.50(3)

V-C(l) 2.09(2) C(l l)-C(12) 1.53(3)

V-0(2) 2.16(2) C(12)-C(13) 1.54(3)

0(1)-C(4) 1.45(3) C(15)-C(16) 1.44(3)

0(1)-C(3) 1.49(3) C(15)-C(20) 1.37(3)

0(2)-C(6) 1.42(3) C(16)-C(17) 1.37(3)

0(2)-C(9) 1.41(2) C(17)-C(18) 1.32(3)

N(l)-C(12) 1.26(3) C(18)-C(19) 1.49(3)

N(l)-C(20) 1.46(2) C(19)-C(20) 1.42(3)

N(2)-C(10) 1.33(2) C(21)-C(22) 1.41(2)

N(2)-C(26) 1.51(2) C(21)-C(26) 1.41(2)

C(2)-C(3) 1.74(4) C(22)-C(23) 1.36(2)

C(4)-C(5) 1.26(4) C(23)-C(24) 1.35(3)

C(6)-C(7) 1.34(3) C(24)-C(25) 1.23(2)

C(7)-C(8) 1.64(5) C(25)-C(26) 1.50(2)

Bond Angle Angle (deg.) Bond Angle Angle (deg.1

N(2)-V-N(l) 89.1(6) C(6)-C(7)-C(8) 97(2)

N(2)-V-0(l) 134.4(6) C(9)-C(8)-C(7) 106(2)

N(l)-V-0(1) 89.6(6) C(8)-C(9)-0(2) 110(2)

N(2)-V-C(l ) 95.7(10) N(2)-C(10)-C(l l) 120(2)

N(l)-V-C(l) 91.9(9) N(2)-C(10)-C(14) 119(2)

0(1)-V-C(1 ) 129.9(10) C(l l )-C(10)-C(14) 120(2)

N(2)-V-0(2) 98.0(6) C(10)-C(l l)-C(12) 129(2)

N(l)-V-0(2) 171.0(6) N(l)-C(12)-C(13) 126(2)

0(l)-V-0(2) 81.4(5) N(l)-C(12)-C(l l) 116(2)

C(l)-V-0(2) 92.9(9) C(13)-C(12)-C(l l) 117(2)

C(4)-0(l )-C(3) 109(2) C(16)-C(15)-C(20) 118(3)

C(4)-0(l)-V 118.3(13) C(17)-C(16)-C(15) 123(2)

C(3)-0(l)-V 131(2) C(16)-C(17)-C(18) 122(2)

C(6)-0(2)-C(9) 105(2) C(19)-C(18)-C(17) 118(2)

C(6)-0(2)-V 122.7(12) C(18)-C(19)-C(20) 119(2)

C(9)-0(2)-V 132.3(13) C(19)-C(20)-C(15) 120(2)

C(12)-N(l)-C(20) 111(2) C(19)-C(20)-N(l) 119(2)

C(12)-N(l)-V 132(2) C(15)-C(20)-N(l) 121(2)

C(20)-N(l)-V 116.4(12) C(22)-C(21)-C(26) 119(2)

C(10)-N(2)-C(26) 112.5(14) C(23)-C(22)-C(21) 119(2)

C(10)-N(2)-V 131.3(14) C(22)-C(23)-C(24) 119(2)

C(26)-N(2)-V 116.0(11) C(25)-C(24)-C(23) 125(2)

0(1)-C(3)-C(2) 106(2) C(26)-C(25)-C(24) 120(2)

C(5)-C(4)-0(l) 128(3) C(25)-C(26)-C(21) 115(2)

C(7)-C(6)-0(2) 1 17(2) C(25)-C(26)-N(2) 126.0(14)

C(21)-C(26)-N(2) 119(2) 46

Table 5A.3 Structure Determination Summary for

[(Ph)₂nacnacVMe(Et₂O)(THF)][B(C₆H₃(CF₃)₂)₄]

Crystal Data Formula C₅₈H₅oBF₂₄N₂O₂V Formula Weight 1324.75 Crystal color Orange-brown block Crystal Size (mm) 0.05 x 0.20 x 0.40 Crystal System monoclinic Space Group Cc Unit Cell Dimensions a = 20.1893(1 1) A b = 15.6580(11) A c = 20.1295(13) A α = 90° β = 106.893(2)° γ= 90°

Volume 6088.8(7) A³

Z 4

Density (calc.) 1.445 g/cm³

Absorption Coefficient 2.79 cm^"1

F(000) 2688

Data collection

Diffractometer Siemens P4

Radiation MoKα (1 = 0.71073 A)

Temperature 293(2) K

Monochromator Highly oriented graphite crystal

20 Range (w) 3.34 to 56.46° Scan type Omega, Phi Scan Range 0.3° Index Ranges -25 <h < 26 0 < k < 20 -25 < 1 < 26

Reflections Collected 8943 Independent Reflections 17489 (R_in. = 10.94%) Observed Reflections 4631 47

Solution and Refinement

System Used SHELXTL (5.03) Solution Direct Methods

Refinement Method Full-Matrix Least-Squares Quantity minimized S[w(Fo² - F_c ²)²]/S[(wFo²)²]^,/2 Hydrogen Atoms Idealized contributions Weighting Scheme w^"' = s²(F) + 0.0010 Final R Indices (obs. data) R = 14.8%, wR = 30.9% R Indices (all data) R = 24.9%, wR = 37.5% Goodness-of-Fit 1.800 Data-to-Parameter Ratio 1 1.1: 1 Largest Difference Peak 2.565 Largest Difference Hole -0.531

48

EXAMPLE 5B

Preparation of 2,4-pentane di(N-phenyl)iminato methyl fos-diethylether vanadium tetrαA ιs^,-(3,5-6wtrifluoromethylphenyl)borate,

[(Ph)₂nacnacVMe(Et₂O)₂][B(C₆H₃(CF₃)2)₄]:

Before the reaction, the drybox was flushed for 30 minutes in an attempt to remove all of the THF from the inert atmosphere. The same reaction sequence and the same reactant quantities as in Example 5A were followed for the synthesis of (Ph)2nacnacVMe(Et₂O)₂[B(C₆H₃(CF3)2)₄]. Orange crystals of were isolated in moderate yield (195 mg, 46 % yield) from a concentrated diethylether solution cooled to -30°C, and based on the analytical data shown in Table 5B the product is believed to contain [(Ph)₂nacnacVMe(Et2O)₂][B(C₆H3(CF₃)2)₄].

TABLE5B ANALYTICAL DATAFOR

[(Ph)₂nacnacVMe(Et₂θ)₂][B(C₆H₃(< CF₃)₂)₄]

'H NMR (C₆D₆) ^a. 123.95 7.60 4.39 -16.75 *** *** *** δ (ppm) (6H,vb) (4H) (6H) (lH.vb)

IR - KBr^b: (cm ') 308 lw 2977w 2936w 2907w 2882w 1610w 1437w

1355vs 1279vs 1 126m 1027w 945w 887m 839m

798w 771w 744w 713m 682m 448w ***

UV-vιs (Et₂0) ^c: 776(266 M 'cm^"') 629(421 M 'cm^"1) 469(1400 M 'cm^" ') λma (ε) μeff 3.1(std. dev. 1), μ_B (294K)

Melting Pt. Range: 89-93°C I

C₅₈H,₂N₂0₂F₂₄VB '

Calculated: (%) C 52.48 H 3.95 N 2.l l -

Measured: ( ) C 49.41 H 3.47 N 2.l l

49

EXAMPLE 6

Preparation of bis-( 2,4-pentane di(N-phenyl)iminato) chromium(II), ((Ph)₂nacnac)₂Cr:

Preparation 1 : Reaction of 2-N-phenylamino-4-N'-phenylimino-3-pentenyl dichloro b/s-tetrahydrofuran chromium, (Ph)₂nacnacCrCl₂(THF)₂, with MeLi:

1.16 mmoles (600 mg) of (Ph)₂nacnacCrCl₂(THF)₂, reference Example

IC, was dissolved in THF and cooled to -30°C. 2 molar eq. of a MeLi solution was added dropwise to the (Ph)₂nacnacCrCl₂(THF)₂ solution. Upon addition of the MeLi solution, the suspension rapidly turned to brown. After the reaction mixture was allowed to stir at room temperature for 4 hours, the solution was evaporated to dryness. THF was removed by trituration in ether.

The resulting solid was extracted with ether and filtered to remove LiCl. The black-green filtrate was then concentrated and cooled to -30°C for crystallization. 210 mg (35% yield) of ((Ph)₂nacnac)₂Cr black green crystals of were isolated.

The resulting compounds were analytically tested and the results are shown in Tables 6A.1-3. The single crystal X-ray diffraction results are shown in Fig. 6.

Preparation 2: Reaction of 2-N-Phenylamino-4-N'-Phenylimino-2-Pentene,

(Ph)₂nacnacH, with MeLi and CrCl₂:

16 mmoles (4.0 g) of (Ph)₂nacnac(H) was dissolved in THF and cooled to -30°C. 16 mmoles (352 mg) MeLi was added to the THF solution of (Ph)₂nacnacH. Using an addition funnel, the THF - (Ph^nacnacLi solution was added dropwise, over a one hour period, to 8 mmoles (983 mg) of CrCl₂ in a THF solution. The reaction mixture was then allowed to stir at room temperature overnight. The solvent was removed to dryness and extracted with diethylether. The extract was then filtered to remove LiCl . 7.09 mmoles 50

(3.7 g, 84% yield) of black ((Ph)₂nacnac)₂Cr crystals were isolated from a concentrated diethylether solution that was cooled to -30°C.

TABLE 6.1

ANALYTICAL DATA FOR ((Ph)₂nacnac)₂Cr

Η NMR (C₆D₆)^a: 123.95 7.60 4.39 -16.75 *** ### *** δ (ppm) (6H,vb) (4H) (6H) (lH,vb)

IR - KBr^b: (cm ¹) 3055w 3029w 2922w 2879m 1591w 1540s 1515m

1482s 1449m 1382vs 1276w 1264w 1021m 866w

842w 752w 700m *** *** *** ***

Mass Spectrometry: 550.22(100) [M⁺] 301.05(45.75) m/z (%) [M⁺ - C1₇H₁₇N₂]

UV-vis (Et₂0)^c: 348(shoulder) λma (ε) (10,444.5 M^"'cm^"')

Heff 5.1(std. dev. 1), μ„ (294K)

Melting Point: 220°C

C₁₄H₃₄N₄Cr

Calculated: (%) C 74.15 H 6.23 N 10.18

Measured: (%) C 72.42 H 6.30 N 10.01

51

Table 6.2 Interatomic Distances and Angles for ((Ph)₂nacnac)₂Cr

(Note: the bond designations are with reference to FIG. 6 and the values noted in parentheses after the distances and angles represent the estimated standard deviation.)

Bond Distance (A) Bond Distance (A)

Cr-N(2) 2.049(4) C( 12)-C(17) 1.381 (6)

Cr-N(3) 2.055(4) C(12)-C(13) 1.406(7)

Cr-N(l ) 2.058(3) C(13)-C(14) 1.375(9)

Cr-N(4) 2.069(3) C(14)-C(I5) 1.353(9)

N(l )-C(2) 1.336(5) C(15)-C(16) 1.392(7)

N(l)-C(l l ) 1.451 (5) C(16)-C(17) 1.380(6)

N(2)-C(4) 1.314(5) C(18)-C(19) 1.522(6)

N(2)-C(17) 1.432(5) C(19)-C(20) 1.389(6)

N(3)-C(19) 1.323(5) C(20)-C(21 ) 1.381(6)

N(3)-C(28) 1.431(5) C(21 )-C(22) 1.505(6)

N(4)-C(21) 1.339(5) C(23)-C(24) 1.378(7)

N(4)-C(34) 1.424(5) C(23)-C(28) 1.385(6)

C(l)-C(2) 1.515(6) C(24)-C(25) 1.372(9)

C(2)-C(3) 1.401(6) C(25)-C(26) 1.359(8)

C(3)-C(4) 1.406(6) C(26)-C(27) 1.376(7)

C(4)-C(5) 1.513(6) C(27)-C(28) 1.393(6)

C(6)-C(7) 1.377(6) C(29)-C(30) 1.377(6)

C(6)-C(l l) 1.379(6) C(29)-C(34) 1.398(6)

C(7)-C(8) 1.379(8) C(30)-C(31 ) 1.388(7)

C(8)-C(9) 1.363(7) C(3 I )-C(32) 1.387(7)

C(9)-C(10) 1.378(7) C(32)-C(33) 1.383(7)

C(10)-C(l l) 1.380(6) C(33)-C(34) 1.398(6)

Bond Angle Angle (deg.) Bond Angle Angle (deg.)

N(2)-Cr-N(3) 149.78(14) C(10)-C(l l)-N(l ) 121.3(4)

N(2)-Cr-N(l) 88.47(14) C(17)-C(12)-C(13) 120.0(5)

N(3)-Cr-N(l) 105.49(14) C(14)-C(13)-C(12) 119.8(5)

N(2)-Cr-N(4) 100.69(14) C(15)-C(14)-C(13) 1 19.7(5)

N(3)-Cr-N(4) 89.35(14) C(14)-C(15)-C(16) 121.4(6)

N(l)-Cr-N(4) 132.88(14) C(17)-C(16)-C(15) 1 19.7(5)

C(2)-N(l)-C(l l) 1 17.3(3) C(12)-C(17)-C(16) 1 19.3(4)

C(2)-N(l)-Cr 121.6(3) C(12)-C(17)-N(2) 123.3(4)

C(l l )-N(l)-Cr 119.2(3) C(16)-C(17)-N(2) 1 17.2(4)

C(4)-N(2)-C(17) 122.9(4) N(3)-C(19)-C(20) 123.6(4)

C(4)-N(2)-Cr 126.2(3) N(3)-C(19)-C(18) 1 19.3(4)

C(17)-N(2)-Cr 1 10.9(3) C(20)-C(19)-C(18) 117.2(4)

C(19)-N(3)-C(28) 119.9(4) C(21 )-C(20)-C(19) 128.7(4)

C(19)-N(3)-Cr 125.5(3) N(4)-C(21 )-C(20) 123.8(4)

C(28)-N(3)-Cr 1 14.1(3) N(4)-C(21)-C(22) 120.1(4)

C(21)-N(4)-C(34) 118.9(4) C(20)-C(21 )-C(22) 116.0(4)

C(21)-N(4)-Cr 123.1(3) C(24)-C(23)-C(28) 120.0(5)

C(34)-N(4)-Cr 1 17.0(3) C(25)-C(24)-C(23) 120.7(5)

N(l)-C(2)-C(3) 123.8(4) C(26)-C(25)-C(24) 1 19.2(5)

N(l)-C(2)-C(l ) 1 19.7(4) C(25)-C(26)-C(27) 121.7(6)

C(3)-C(2)-C(l) 1 16.5(4) C(26)-C(27)-C(28) 119.3(5)

C(2)-C(3)-C(4) 128.0(4) C(23)-C(28)-C(27) 1 19.1(4)

N(2)-C(4)-C(3) 121.9(4) C(23)-C(28)-N(3) 1 18.8(4)

N(2)-C(4)-C(5) 121.5(4) C(27)-C(28)-N(3) 122.1(4)

C(3)-C(4)-C(5) 116.6(4) C(30)-C(29)-C(34) 121.2(4)

C(7)-C(6)-C(l l ) 121.1(5) C(29)-C(30)-C(31 ) 120.3(4)

C(6)-C(7)-C(8) 1 19.6(5) C(30)-C(31 )-C(32) 1 19.5(5)

C(9)-C(8)-C(7) 1 19.7(5) C(33)-C(32)-C(31 ) 1 19.8(5)

C(8)-C(9)-C(10) 120.8(5) C(32)-C(33)-C(34) 121.5(4)

C(9)-C(10)-C(l l ) 120.2(5) C(33)-C(34)-C(29) 1 17.6(4)

C(6)-C(l l )-C(10) 1 18.6(4) C(33)-C(34)-N(4) 122.2(4)

C(6)-C(l l )-N(l ) 120.0(4) C(29)-C(34)-N(4) 120.1 (4) 52

Table 6.3 Structure Determination Summary for((Ph)₂nacnac)₂Cr

Crystal Data Empirical Formula C₃₄H₃₄N₄Cr Formula Weight 550.65 Crystal color Dark green plates Crystal Size (mm) 0.40 x 0.40 x 0.06 Crystal System triclinic Space Group PI

Unit Cell Dimensions a = 10.54650(10) A b = 1 1.4442(2) A c = 13.8021(2) A α =87.5203(9)° β = 72.7442(8)° γ= 65.33°

Volume 1439.44(5) A

Z 2

Density (calc.) 1.270 g/cm³

Absorption Coefficient 4.27 cm^"1

F(000) 580

Data collection Diffractometer Used Siemens P4 Radiation MoKα (1 = 0.71073 A) Temperature 218(2) K Monochromator Highly oriented graphite crystal

2Θ Range (w) 3.10 to 56.60° Scan type Omega, Phi Scan Range 0.3° Index Ranges -13 <h < 13 -14 < k < 14 0 < 1 < 18

Reflections Collected 6231 Independent Reflections 6231 (R_ιnt = 0.0000%) Observed Reflections 4039 53

Solution and Refinement

System Used SHELXTL (5.03) Solution Direct Methods

Refinement Method Full-Matrix Least-Squares Quantity minimized S[w(F₀ ² - F_c ²)²]/S[(wFo²)²]^{1 2} Hydrogen Atoms Idealized contributions Weighting Scheme w^"' = s²(F) + 0.0010 Final R Indices (obs. data) R = 8.87%, wR = 21.76% R Indices (all data) R = 1 1.77%, wR = 24.49% Goodness-of-Fit 1.100 Data-to-Parameter Ratio 17.7: 1 Largest Difference Peak 0.892 Largest Difference Hole -0.812

Polymerization Experiments

Method For Determining M„, M_n. M» & M_p

The M_w, weight average molecular weight, M_n, number average molecular weight, weighted to the low end of the material, M_z, average weighted to the high end of the material, and M_p, the peak position molecular weight for the polymer samples are determined using Size Exclusion Chromatography (SEC) columns. SEC columns separate a polymer solution into fractions based on their 3-dimensional molecular size (hydrodynamic volume - Hv). These fractions are detected by a refractive index (RI) detector which responds linearly to the concentration of homogenous polymers. The molecular weight distribution (MWD) is then determined as the linear equivalent molecular weight relative to a linear calibration polyethylene (PE) standard (Chevron 9640). For high density PE (HDPE), the molecular weights determined can be considered an absolute quantity. For low density PE (LDPE), the average molecular weight (M_w) is underestimated proportionately to the additional weight of branches along the backbone. For samples 54

containing a fairly consistent amount of branching, molecular weight distributions can be compared on a relative scale to each other.

Samples of the polymer are ground up to a 20 mesh size. 8mg +/- 0.2mg are weighed into a 4 ml vial with three separate preparations per measurement. 4mL of TCB (with 500ppm antioxidant to prevent molecular decomposition) is added with an automatic solvent dispenser to each vial.

Samples are dissolved in a oven for 4 Hours at 180°C. The vials are shaken 3 times over this 4 hour period. The sample are then tested using a Waters 150C Chromatography System equipped with 3 Mixed A + 1 50A Polymer

Laboratories (UK) Columns. The measurements are conducted under the following conditions:

Concentration: 2mg/mL Injection Volume: 400uL Flowrate: lmlJmin

Column and Injector Compartment Temperature: 150C Run Time: 1 Hour

The Method of Calculation is: Weight fraction of polymer is weighted against molecular weight with Flow Rate Correction employed by referencing flow rate marker peak. The ViscoTek:TriSec Software Conventional Calibration Module ver. 3.00 is used to report M_n, M_w, M_z, M_p, and D average for the three separate preparations.

Method For Determining Short Chain Branching (SCB)

Samples were analyzed on a Varian Unity+ NMR spectrometer at a magnetic field of 7 Tesla with a 10mm broadband probe tuned for C-13. Approximately 0.5g of sample was placed in a 10mm NMR tube and filled with 3ml of a 3: 1 1 ,2,4-trichlorobenzene / deuterated benzene mixture. The sample is warmed to 130°C and allowed to dissolve until a clear solution is formed. When bubbles and voids in the viscous solution have been 55

eliminated, the sample is ready for analysis. The sample is placed in the bore of the NMR magnet and heated to 130°C. The sample is allowed to come to thermal equilibrium and stabilize for 5 minutes. The sample is deuterium locked on to the deuterated benzene signal for magnet field stability and the sample's magnetic field is shimmed to reduce magnetic field inhomogeneities in order to increase resolution and the signal to noise ratio. The sample is pulsed every 5.9 seconds (0.9s acquisition time and 5s recycle delay for relaxation) for 2500 total transients making a total experiment time of 4 hours. The recorded free induction decay is Fourier transformed to yield the NMR spectrum. The spectrum is then phased and baseline corrected. The short chain branching content is determined using specific resonances that are characteristic and unique to each type of short chain branch (methyl through hexyl and longer). The ratio of the integrals of each characteristic resonance with the resonance for the polymer backbone (27.8 to 31.5 ppm) is taken and the ratio is reported as short chain branches per 1000 carbons. Low molecular weight carbon content is determined by the ratio of the integral of the characteristic resonance at 114 ppm to the integral of the polymer backbone.

Method For Determining Melting Point (Peak DSC M.P.)

Samples were analyzed on a Perkin-Elmer DSC7 differential scanning calorimeter with an intercooler attachment. The sample size of approximately lOmg was placed in an aluminum pan and an aluminum lid was crimped on. The sample is heated twice, the first time to eliminate thermal history and the second time where the DSC sample measurement is recorded. The sample is heated from 0°C the first time to 170°C at 20°C/min, held for 5 minutes at

170°C, then control cooled at 10°C/min to 0°C. The sample is held at 0°C for 1 minute then reheated at 20°C/min to 170°C. This second heating scan is recorded. The peaks are used to determine the melting points which generally 56

appear between 90 to 140°C. The area under the curve is considered to be the heat of fusion of the polyethylene copolymer.

The following polymerization that resulted in formation of oligimers were characterized using an HP 5890 Gas Chromatograph fitted with a FID Detector, Helium Carrier Chrompack Column: WCOT ulti-metal 10M X0.53MM coating HT SIMDIST CBDF=0.15 UM. At the following conditions: 120°C x lmin x 10°C/min x 150°C x 0 min and RampA: 6.0°C/min x 350°C x Omin.

EXAMPLE 7

Polymerization of Ethylene in a NMR Tube Reaction in the Presence Of in-situ (Ph)₂nacnacVMe₂[B(C₆F₅)₃]_:

Preparation 1 (in CD_?CM:

0.0453 mmoles (15 mg) of (Ph)₂nacnacVMe₂, reference Example 3 A, and 0.0453 mmoles (23 mg) of B(C₆F₅)₃ were transferred to an NMR tube reactor and CD₂CI₂ was vacuum transferred. Ethylene (@ 1 atm.) was charged to the NMR tube and it was closed with a Teflon tap. After 5 minutes, a 1H NMR spectrum was recorded. Only the ethylene resonance (6 5.40 ppm) and a new peak δ 1.7 ppm was added to the original spectrum, reported in example 3 A above. After 10 minutes, white particles of polyethylene had precipitated out of the solution. One more charge of ethylene (@ 1 atm) was added to the

NMR tube and allowed to react for three hours. Another Η NMR reading was taken and the spectrum had all the resonances associated with the catalyst while the ethylene monomer peak had nearly disappeared.

Preparation 2 (in C λ): 57

Polymerization of ethylene was also tried in an NMR tube with 4.53x 10^"5 moles (15 mg) of, reference Example 3 A, and 4.53x 10^"5 moles (23 mg) of B(C₆F₅)₃. Upon condensing C D₆, (Ph)₂nacnacVMe₂ and B(C₆F₅)₃ reacted to give a brown black oil which was not soluble in C₆D₆. After one day at room temperature, the ethylene monomer peak had decreased to approx. 40% (integrated to C6D6 peak) Η NMR (C₆D₆): broad peaks from 2.4 to 0.6 ppm.

EXAMPLE 8

Polymerization Of Ethylene in a Parr Reactor in the Presence of (Ph)₂nacnacVMe₂ and Cocatalyst in CH₂C1₂:

0.151 mmoles (50 mg) of (Ph)₂nacnacVMe2, reference Example 3a, and 0.151 mmoles of B(C₆F₅)₃ (77 mg) were dissolved in 100 ml of CH C1₂ and the solution was placed in a Parr reactor. Ethylene (@700 psig) was charged to the reactor. After about five minutes, the ethylene supply was closed because the temperature of the reactor had reached 120°C. The pressure decreased steadily with stirring. After stirring for several hours, the reactor was opened to atmosphere. Dark colored polymer was found in blocks.

The blocks were washed with a methanol/HCl mixture and deionized (Dl) water and then dried in a vacuum oven at 60°C overnight. 5.2 grams of polymer were collected. Polymer analysis: M_w = 547,700; M_w/M_n= 2.06; Peak DSC M.P.: 134.2°C.

EXAMPLE 9

Polymerization Of Propylene in a NMR Tube Reactor in the Presence of (Ph)₂nacnacVMe₂ and Cocatalyst in CD2CI2:

4.53x10-5 moles(15 mg) of (Ph)2nacnacVMe₂, reference Example 3a, and 4.53x10-5 moles (23mg) of B(C₆F₅)₃ were dissolved in CD₂C1₂ and placed in a NMR tube reactor. Propylene (@ 1 atm.) was then charged to the NMR 58

tube reactor. When a Η NMR spectrum was recorded after 10 minutes, there was no indication of reaction. Η NMR spectra obtained after several hours at room temperature and after heating to 60°C overnight, continued to show no reaction.

EXAMPLE 10

Polymerization of 1-Hexene in a NMR Tube Reactor in the Presence of (Ph)₂nacnacVMe₂ and Cocatalyst in CD₂CI₂:

(Ph)₂nacnacVMe₂[B(C₆F₅)₃] was prepared as described above, reference Example 9. 1-hexene (pre-dried over Na K alloy) was vacuum transferred to a NMR tube reactor. A Η NMR spectrum was recorded after 10 minutes and then the NMR tube was heated to 60°C overnight. Analysis of the resulting product indicated formation of oligomers, mostly dimers to hexamers, including branched oligomers.

EXAMPLE 11

Copolymerization of Ethylene and 1-Hexene in a Parr Reactor in the

Presence of (Ph)₂nacnacVMe₂ and Cocatalyst in CH2CI2:

0.151 mmoles (50 mg) of (Ph)₂nacnacVMe2, reference Example 3a, and 0.151 mmoles of B(C₆F₅)₃ (77 mg) were dissolved in a solvent mixture of 60 ml of CH₂CI₂ and 30 ml of 1-hexene. The solution was placed in a Pan- reactor. Ethylene (@800 psig) was charged to the reactor. Then the ethylene supply was closed because the temperature of the reactor reached nearly 120°C. With stirring, the pressure decreased steadily. After stirring for several hours, the reactor was opened and blocks of polymer were observed. The blocks were washed with a methanol/HCl mixture and deionized (Dl) water and then dried in a vacuum oven at 60°C overnight. 5.2 grams of polymer were collected. Polymer analysis: M_w = 1,136,000; M_w/M_n = 2.42; Peak DSC M.P: 131.4°C;. ¹ C NMR: no side chains were indicated. 59

EXAMPLE 12

Polymerization of Ethylene in a NMR Tube Reactor in the Presence of [(Ph)₂nacnacVMe(Et₂O)(THF)][B(C₆H₃(CF₃)₂)₄] in CD₂C1₂:

1.88xl0^"5 moles (25 mg) [(Ph)₂nacnacVMe(Et₂O)(THF)][B(C₆H₃(CF₃)₂)₄], reference Example 5A, in CD₂CI₂ was introduced into a NMR tube reactor. Ethylene (@ 1 atm.) was charged into the NMR tube and the Teflon tab was closed. After 15 minutes, a fine precipitate of polyethylene was visible and a Η NMR spectrum recorded trace amounts of free diethylether peaks along with an intense ethylene monomer peak at δ 5.40 ppm. After allowing the reaction to stand overnight at room temperature, several particles of polymer were visually observed and

Η NMR spectrum recorded free diethylether resonances and trace amounts of unreacted ethylene monomer. This reaction was run an additional two times substituting propylene (@ 1 atm.) and 1-hexene for ethylene and no polymerization was observed even with heating.

EXAMPLE 13

Polymerization of Ethylene in a Parr Reactor in the Presence of [(Ph)2nacnacVMe(Et₂O)(THF)][B(C₆H₃(CF₃)2)₄] in CH₂C1₂:

0.045 mmoles (60mg) [(Ph)₂nacnacVMe(Et₂O)(THF)][B(C₆H₃(CF₃)₂)₄], reference Example 5 A, dissolved in 100 ml of CH2CI₂ was introduced into a Parr reactor. Ethylene (@700 psig) was supplied to the reactor. Once the reactor was pressurized, the ethylene supply was shutoff. With stirring, the ethylene pressure decreased slowly. After stirring for several hours, the reactor was opened to atmosphere. After stirring for several hours, the reactor was opened and blocks of polymer were observed. The blocks were washed with a methanol/HCl mixture and 60

deionized (Dl) water and then dried in a vacuum oven at 60°C overnight. 2.5 g of polymer were collected. Polymer analysis: M_w = 450,600; M_w M_n = 1.96; and Peak DSC M.P: 135.9°C.

EXAMPLE 14

Polymerization of Ethylene in a Parr Reactor in the Presence of (Ph)₂nacnacVCl₂(THF)₂ and Cocatalyst in CH₂C1₂:

0.776 mmoles (40mg) of (Ph)₂nacnacVCl₂(THF)₂, reference Example

IB, was dissolved in 100 ml of dry CH₂C1₂ in a Parr reactor. The color of the solution turned brown. Upon addition of 7.3g (approx. 100 molar eq.) of MAO, 10 wt.% solution in toluene, the color of the solution instantaneously changed to dark red brown. Ethylene (@400 psig) was supplied to the reactor. Once the reactor was pressurized, the ethylene supply was shutoff. Pressure decreased slowly with stirring. After stirring for several hours, the reactor was opened and blocks of polymer were observed. The blocks were washed with a methanol/HCl mixture and deionized (Dl) water and then dried in a vacuum oven at 60°C overnight. 4.6 g of polymer were collected. Polymer analysis: M_w = 350,032, M_w M_n = 10.84.

EXAMPLE 15

Polymerization of Ethylene in a Parr Reactor in the Presence of

(Ph)₂nacnacVCl₂(THF)₂ and Cocatalyst in Toluene:

1.20 x 10^"5 moles (8mg) of (Ph)₂nacnacVCl₂(THF)₂, reference Example IB, was dissolved in 50 ml of toluene in a Parr reactor and 1.2 g (approx. 100 molar eq.) of MAO, 10 wt.% solution in toluene, was added to the solution. Polymerization was performed under a constant pressure of ethylene (@ 300 psig) for 1 hour, after which the ethylene supply was closed. The reaction was allowed to continue for an additional 1/2 hour to monitor further ethylene uptake. During the 1/2 hour, the ethylene pressure decreased 61

by 50 psi. The reaction temperature was maintained under 60°C by cooling water circulation system. The resulting product was washed with a methanol/HCl mixture and deionized (Dl) water and then dried in a vacuum oven at 60°C overnight. 4.7 g of white polyethylene polymer was collected. Polymer Polyethylene analysis: M_w = 1 ,958,584; M_w/M_n = 1.75; and Peak

DSC M.P : 135.4°C

COMPARATIVE EXAMPLE 1

Polymerization of Ethylene in a Parr Reactor in the Presence of

VCI₃(THF)₃ and Cocatalyst inToIuene:

1.20xl0^"4 moles (6 mg) of VC1₃(THF)₃ was dissolved in 50 ml of toluene in a Parr reactor. The color of the solution turned brown and VC1₃(THF)₃ was somewhat soluble. Upon addition of 1.2g (approx. 100 molar eq.) of MAO, 10 wt.% solution in toluene, the color of the solution instantaneously changed to dark red brown. The reaction was allowed to proceed for 1.5 hours under the constant pressure of ethylene (@ 300 psig), after which the ethylene supply was closed to monitor ethylene uptake. A 0.5 hour after the ethylene supply was closed, the pressure had decreased by 130 psi. Over the course of the reaction, the reaction temperature was maintained under 60°C with a water circulation pump. The resulting product was washed with a methanol/HCl mixture and deionized (Dl) water and then dried in a vacuum oven at 60°C overnight. 8.0 g of white polyethylene granules were collected. Polymer analysis: M_w = 2,042, 158; M_w/M_n = 1.73 and Peak DSC

M.P: 132.TC.

62

EXAMPLE 16

Copolymerization of Ethylene and 1-Hexene in a Parr Reactor in the presence of (Ph)₂nacnacVCl₂(THF)₂ And Cocatalyst in CH₂C1₂:

7.76 x 10^"5 moles (40 mg) of (Ph)₂nacnacVCl₂(THF)₂, reference

Example IB, was dissolved in 100 ml of CH₂CI₂ and 7.3g (approx. 100 molar eq.) MAO, 10 wt.% solution in toluene, was added to the solution and placed in a Parr reactor. 40 ml of dry 1-hexene was added to the reaction mixture. Ethylene (@350 psig) was introduced into the reactor and the ethylene supply was closed. After one minute, the temperature had increased to 52°C. The temperature then decreased slowly and stayed at 45°C. The reactor was stirred for an hour. When the reactor was opened to the atmosphere, the entire reactor was filled with white sticky polymer. The resulting product was washed with a methanol/HCl mixture and deionized (Dl) water and then dried in a vacuum oven at 60°C overnight. 23.6 g of polymer were collected. Polymer analysis: M_w =707,048; M_w M_n = 212.33; and total carbons on side chain/1000 carbons by ^, C NMR: 48.3.

EXAMPLE 17

Polymerization of 1-Hexene in the Presence of (Ph)₂nacnacV(Me)₂ and Cocatalyst in CH₂C1₂: 6.04 x 10^"5 moles (20 mg) of (Ph)₂nacnacV(Me)2, reference Example

3 A, was dissolved in 40 ml of dry CH₂C1₂ in an ampoule. MAO (approx. 100 molar eq. in toluene) was added into the solution of (Ph)2nacnacV(Me) in the ampoule and the ampoule was closed with a Teflon tap. After two cycles of freeze/pump/thaw, approx. 5 ml of 1-hexene was condensed into the ampoule. When the reaction mixture was stirred at room temperature for two hours, there was no apparent change in color or viscosity of the reaction mixture. The oil bath temperature was elevated to 80°C and stirred overnight. The solution turned dark orange and became very viscous when cooled down to 63

room temperature. The ampoule was opened to atmosphere and a MeOH/HCl solution was added to wash the resulting product. However, the dark orange color was not removed. All the volatile species were removed by distillation leaving a very dark brown oil. Polymer analysis: Η NMR (CDCπ): broad peaks at δ 2.1 , 1.3, 1.2, 0.8 ppm. Analysis of the resulting product indicated formation of oligomers, mostly dimers to hexamers, which included branched oligomers.

EXAMPLE 18

Polymerization of Ethylene in the Presence of (Ph)₂nacnacTiCl₂(THF)₂ and Cocatalyst in CH2CI₂:

3.91 x 10^"5 moles (20mg) of (Ph)₂nacnacTiCl₂(THF)₂, reference

Example 1 A, was dissolved in 50 ml of CH₂CI2 in a 100 ml Schlenk flask equipped with a stirring bar. 7.3g of MAO, 10 wt. % in toluene, was added to the brown solution of (Ph)₂nacnacTiCl₂(THF)₂ and Teflon stopper equipped with a needle valve was attached. After two cycles of freeze/pump/thaw, ethylene (@ 1 atm.) was introduced into the flask at room temperature. Every five minutes over a 1 hour period, the decrease in pressure was monitored. A white powder of polyethylene (160 mg) was produced in one hour. Polymer analysis: M_w = 195,015, M_w/M_n = 21.11; and M.P by DSC=130.6°C

EXAMPLE 19

Polymerization of Ethylene in a Parr Reactor in the Presence of (Ph)₂nacnacTiCl₂(THF)₂ and Cocatalyst in CH₂C1₂: 1.57 x 10^"5 moles (8 mg) of (Ph)₂nacnacTiCl₂(THF)₂, reference 1 A, was dissolved in 50 ml of CH₂C1₂ and 1.2g (approx. 100 molar eq.) of MAO, 10 wt.% solution in toluene, was added to the solution and the solution was placed into a Parr Reactor. The reaction was allowed to proceed for 1 hour under the constant pressure of ethylene (@ 300 psig), after which the ethylene 64

supply was closed and the ethylene pressure decrease was monitored over the next 0.5 hour. However, there was no further decrease in ethylene pressure. The resulting product was washed with a methanol/HCl mixture and deionized (Dl) water and then dried in a vacuum oven at 60°C overnight. 6.1 g of white polyethylene granules were isolated. Polymer analysis: M_w = 685,963; M_w/M_n

= 30.9; and M.P by DSC=132.2°C

EXAMPLE 20

Copolymerization of Ethylene and 1-Hexene in a Parr Reactor in the

Presence of (Ph)₂nacnacTiCl₂(THF)₂ and Cocatalyst in CH₂CI₂:

3.90 x 10^"5 moles (20mg) of (Ph)₂nacnacTiCl₂(THF)₂, reference Example IA, and 8.0 g (approx. 200 molar eq.) MAO, 10 wt.% solution in toluene, were dissolved in the mixture of 1-hexene (30 ml) and CH₂C1₂ (60 ml). This solution was placed in a Parr reactor. When ethylene (@ 350 psig) was introduced into the reactor, the temperature rapidly increased to 52°C within a minute. The reaction was quenched after 25 minutes since the temperature suddenly increased very rapidly to 140°C. When the reactor was opened to atmosphere, a light brown rubbery polymer was observed. . The resulting product was washed with a methanol/HCl mixture and deionized (Dl) water and then dried in a vacuum oven at 60°C overnight. 12.5 g of polymer were collected. Polymer analysis: M_w = 33,882; M_w/M_n = 218.51 ; and total carbons on side chain/1000 carbons, by ¹³C NMR = 34.6.

EXAMPLE 21

Polymerization of 1-Hexene in the Presence of (Ph)₂nacnacTiCl₂(THF)₂ and Cocatalyst in CH₂C1₂:

The reaction was performed with 3.90x10-5 moles (20 mg) of (Ph)₂nacnacTiCl2(THF) , reference Example IA, MAO (100 eq.) solution and 5 ml of 1-hexene in 20 ml of CH2CI2 in an ampoule sealed with a Teflon 65

stopper. After stirring for two hours at room temperature, the ampoule was allowed to stir at 80°C overnight. The solution turned to dark orange and became very viscous when cooled down to room temperature. The ampoule was opened to atmosphere. The resulting product was washed but the dark orange color was not removed. All the volatile species were removed by distillation to give a very dark brown oil. Analysis of the resulting product indicated formation of oligomers, mostly dimers to hexamers, which included branched oligomers.

EXAMPLE 22

Polymerization of Ethylene in a Parr Reactor in the Presence of (Ph)₂nacnacTiCl₂(THF)₂and Cocatalyst in Toluene:

1.20 x 10^"5 moles (8 mg) of (Ph)₂nacnacTiCl₂(THF)₂, reference

Example 1 A, was dissolved in 50 ml of toluene in a Parr reactor. 1.2 g (approx. 100 molar eq.) of MAO, 10 wt.% solution in toluene, was added to the solution. The reaction temperature was kept below 60°C by circulating cooling water. The reaction proceeded for 1 hour under constant pressure maintained by ethylene (@ 300 psig), after which the ethylene supply was closed. The reaction was continued, with stirring, for another 0.5 hour to monitor further ethylene uptake. During that 0.5 hour, the pressure decreased by 100 psi. The resulting product was washed with a methanol/HCl mixture and deionized (Dl) water and then dried in a vacuum oven at 60°C overnight. 10.5 g of white polyethylene granules were collected. Polymer analysis: M_w =

818,850; M_w/M_n = 28.58; and Peak DSC M.P: 134.2°C.

66

COMPARATIVE EXAMPLE 2

Polymerization of Ethylene in a Parr Reactor in the Presence of TiCl₃(THF)₃, and Cocatalyst in Toluene:

1.20 x 10^"4 moles (6mg) of TiCl₃(THF)₃ was dissolved in 50 ml of toluene in a Parr reactor. 1.2 g (approx. 100 molar eq.) of MAO, 10 wt.% solution in toluene, was added to the TiCl₃(THF)₃ solution. Upon addition of MAO, the color of the TiCl₃(THF)₃ solution changed instantaneously a darker brown. The reaction temperature was kept under 60°C by circulating cooling water. The reaction proceeded for 1 hour under constant pressure maintained by ethylene (@ 300 psig), after which the ethylene supply was closed. The reaction was continued for another 0.5 hour during which the pressure decreased only 25 psi. The resulting product was washed with a methanol/HCl mixture and deionized (Dl) water and then dried in a vacuum oven at 60°C overnight. 3.4 g of white polymer granules were collected. Polymer analysis: M_w = 1,479,060; M_w/M_n = 153.12; Peak DSC M.P: 134.2°C.

EXAMPLE 23

Polymerization of Ethylene in a Parr Reactor in the Presence of (Ph)₂nacnacCrCl₂(THF)₂ and Cocatalyst in CH₂C1₂:

7.76 x 10^"5moles (40 mg) (Ph)₂nacnacCrCl₂(THF)₂, reference Example IC, and 7.3 g (approx. 100 molar eq.) of MAO, 10 wt.% solution in toluene, were dissolved in 100 ml of CH₂C1₂ and the solution was placed in a Parr reactor. Ethylene (@400 psig) was supplied to the reactor. Once the reactor was pressurized, the ethylene supply was shutoff. With stirring, the temperature increased slowly to a maximum of 110°C, after which is decreased slowly. After stirring for 30 minutes, a white powder of polyethylene was obtained. The resulting powder was washed with a methanol/HCl mixture and deionized (Dl) water and then dried in a vacuum 67

oven at 60°C overnight. 6.0 g of white polymer powder was collected. Polymer analysis: M_w = 48,613 and M_w/M_n = 22.84.

EXAMPLE 24

Polymerization of Ethylene in a Parr Reactor in the Presence of (Ph)₂nacnacCrCl₂(THF)₂ and Cocatalyst in Toluene:

1.20 x 10^"5moles (8 mg) (Ph)₂nacnacCrCl₂(THF)₂, reference Example

IC, and 1.2 g (approx. 100 molar eq.) of MAO, 10 wt.% solution in toluene, were dissolved in 50 ml of toluene in a Parr reactor. Ethylene (@300 psig) was supplied to the reactor. After stirring for 1 hour under constant ethylene pressure with cooling, the ethylene supply was closed. Over the course of the following 45 minutes, the ethylene pressure decreased by 100 psi. The resulting product was washed with a methanol/HCl mixture and deionized (Dl) water and then dried in a vacuum oven at 60°C overnight. 10.5 g of a white solid polymer was isolated. Polymer analysis: M_w: 1,157,039; M_w/M_n: 72.81 ; and Peak DSC M.P:134.9°C.

COMPARATIVE EXAMPLE 3

Polymerization of Ethylene in a Parr Reactor in the Presence of CrCI₃(THF)₃and Cocatalyst in Toluene:

1.20 x 10^"4 moles (6mg) of CrCl₃(THF)₃ was dissolved in 50 ml of toluene in a Parr reactor. 1.2 g (approx. 100 molar eq.) of MAO, 10 wt.% solution in toluene, was added to the CrCl₃(THF)₃ solution. Upon addition of MAO, the color of the solution was pale brown even after stirring for 10 minutes and solid CrCl₃(THF)₃ remained. The reaction proceeded for 1 hour under constant pressure maintained by ethylene supplied @300 psig. The ethylene supply was closed and there was no observable pressure decrease over the next 30 minutes. The reaction temperature remained essentially constant, around 23°C, throughout the reaction time, even without cooling. The resulting product was washed with a methanol/HCl mixture and deionized (Dl) water and then dried in a vacuum oven at 60°C overnight. 0.5 g of polyethylene were obtained. Polymer analysis: M_w = 1,319,817; M_w/M_n = 37.88; and Peak DSC M.P: 133.3°C.

EXAMPLE 25

Copolymerization of Ethylene and 1-Hexene in a Parr Reactor in the Presence of (Ph)₂nacnacCr C1₂(THF)₂ and Cocatalyst in CH₂C1₂ :

The reaction was performed with 7.76 x 10^"5 moles (40 mg) of (Ph)₂nacnacCrCl₂(THF)₂, reference Example IC, and 7.5 g (approx. 100 molar eq.) of MAO, 10 wt.% solution in toluene, in a solvent mixture of 40 ml of 1- hexene and 60 ml of CH₂C1₂ in a Parr reactor. Ethylene (@350 psig) was supplied to the Parr reactor in accordance with the procedure set forth in Example 22. 8.7 g of white polymer powder was collected. Polymer analysis: M_w = 9,659, M_w/M_n:= 7, M.P. by DSC = 109.6 and 125.4°C and SCB=16.

EXAMPLE 26

Copolymerization of Ethylene and Propylene in a Parr Reactor in the Presence of (Ph)₂nacnacCrCl₂(THF)₂ and Cocatalyst:

8mg (Ph)nacnacCrCl₂(THF)₂ and 100 molar equivalents of MAO solution was dissolved in 50 ml of toluene in a Parr reactor. A gas mixture of ethylene and propylene (@ 100 psig) was charged into the reactor. After stirring for three hours the reaction was terminated. The resulting product was washed with a methanol/HCl mixture and deionized (Dl) water and then dried in a vacuum oven at 60°C overnight. 250 mg of white rubbery polymer was isolated.

Polymer analysis: M_w = 147,054, M_w/M_n:= 82.14, M.P. by DSC = 95.1,113.8 and 125.1°C, and SCB=9.69. 69

EXAMPLE 27

Polymerization of Propylene in a Parr Reactor in the Presence of (Ph)₂nacnacCrCl₂(THF)₂ and Cocatalyst:

Attempts to polymerize propylene using reaction conditions similar to those set forth resulted in a product that could not be readily characterized using the techniques employed herein. Additional test using the corresponding Vanadium and Titanium catalyst equally provided a product that could not be readily characterized.

EXAMPLE 28

Copolymerization of Ethylene and Propylene in a Parr Reactor in the Presence of (Ph)₂nacnac VC1₂(THF)₂ and Cocatalyst:

8 mg. (Ph)₂nacnacVCl₂(THF)₂ and 100 molar equivalents of MAO solution was dissolved in 50 ml of toluene in a Parr reactor. A gas mixture gas of ethylene and propylene (@ 100 psi) was charged into the reactor. After stirring for three hours the reaction was terminated. After washing and drying 800 mg of white rubbery polymer was isolated. Polymer analysis: M_w = 1,476,492 M_w/M_n:= 3.94, M.P. by DSC = 1 17.4°C, and SCB=14.88.

Having described specific embodiments of the present invention, it will be understood that many modifications thereof will readily appear or may be suggested to those skilled in the art, and it is intended therefore that this invention is limited only by the spirit and scope of the following claims.

Claims

70WHAT IS CLAIMED IS:

1. A catalyst system useful for the polymerization of olefin monomers, said catalyst system comprising a monoanionic bidentate ligand represented by Formula (II): π

R¹> R

/

^ΓûáN

R³ ( ( ╬ÿ

\

R2 R

wherein

R and R' independently represent a hydrogen atom, or a substituted or unsubstituted, branched or unbranched hydrocarbyl or organosilyl radical;

1 9 "^

R , R and R independently represent a hydrogen atom, or a substituted or unsubstituted, branched or unbranched hydrocarbyl radical.

2. The catalyst system of claim 1 wherein said monoanionic ligand is coordinated to a group D3B, IVB, VB, VIB, VIIB or NTH transition metal.

3. The catalyst system of claim 2 wherein said metal is a group F B, VB, or VB3 transition metal. 71

4. The catalyst system of claim 3, wherein said transition metal is selected from the group consisting of titanium, vanadium, and chromium.

5. The catalyst system of claim 1 , wherein R and R' independently represent a hydrogen atom, or a radical selected from the group consisting of alkyl, aryl, alkylaryl, arylorganosilyl, and alkylorganosilyl.

6. The compound of claim 5, wherein said radical includes a carbon atom, directly bound to the nitrogen, having at least two carbon atoms bound thereto.

7. The catalyst system of claim 1 , wherein R and R' independently represent a hydrogen atom, or an ethyl, isopropyl, phenyl, 2,6-isopropylphenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 4-methylphenyl, 2,4,6-trimethylphenyl or 2-t-butylphenyl radical.

8. The catalyst system of claim 1, wherein R¹ and R² independently represent a hydrogen atom, or an alkyl radical having 1-6 carbon atoms.

9. The catalyst system of claim 1 , wherein R¹ and R² independently represent a hydrogen atom or a methyl radical.

10. The catalyst system of claim 1, further comprising a metal alkyl cocatalyst.

11. The catalyst system of claim 10, wherein said co-catalyst is an alkyl aluminum compound.

12. The catalyst system of claim 11, wherein said alkyl aluminum compound includes a trialkylaluminum or an aluminoxane. 72

13. The catalyst system of claim 1 1 , wherein said aluminoxane selected from the group consisting of ethyl aluminoxane, isobutyl aluminoxane, and methyl aluminoxane.

14. The catalyst system of claim 1 1 , wherein said alkyl aluminum compound is triethylaluminum.

15. An compound useful as a catalyst represented by Formula (I):

F?

optionally

wherein

R and R' independently represent a hydrogen atom, or a substituted or unsubstituted, branched or unbranched hydrocarbyl or organosilyl radical;

R¹, R² and R³ independently represent a hydrogen atom, or a substituted or unsubstituted, branched or unbranched hydrocarbyl radical; and

M is a group DIB, rVB, VB, VB, VITB or VH3 transition metal; each T independently represents a univalent anionic ligand such as a hydrogen atom, or a substituted or unsubstituted hydrocarbyl, halogeno, aryloxido, arylorganosilyl, alkylorganosilyl, amido, 73

arylamido, phosphido, or arylphosphido group, or two T groups taken together represent an alkylidene or a cyclometallated hydrocarbyl bidentate ligand; each L independently represents a sigma donor stabilizing ligand; X, which is optional, represents a relatively weakly coordinated anion; and a = 0 to 4 inclusive, b = 0 to 4 inclusive, provided a+b < 4.

16. The compound of claim 15, wherein M is a group 1NB, VB, or VIB transition metal.

17. The compound of claim 15, wherein M is selected from the group consisting of titanium, vanadium, and chromium.

18. The compound of claim 15, wherein R and R' independently represent a hydrogen atom, or a radical selected from the group consisting of alkyl, aryl, alkylaryl, arylorganosilyl, and alkylorganosilyl.

19. The compound of claim 18, wherein said radical includes a carbon atom, directly bound to the nitrogen, having at least two carbon atoms bound thereto.

20. The compound of claim 15, wherein R and R' independently represent a hydrogen atom, or an ethyl, isopropyl, phenyl, 2,6-isopropylphenyl, 2,6- dimethylphenyl, 2,6-diethylphenyl, 4-methylphenyl, 2,4,6-trimethylphenyl or

2-t-butylphenyl radical. 74

21. The compound of claim 15, wherein R¹, R² and R³ wherein independently represent a hydrogen atom or an alkyl radical having 1-6 carbon atoms.

22. The compound of claim 15, wherein R¹, R² and R³ independently represent a hydrogen atom or methyl radical.

23. The compound of claim 15, wherein R³ represents hydrogen.

24. The compound of claim 23, wherein R and R each represent a methyl radical.

25. The compound of claim 15, wherein X represents a BArF^", (phenyl)₄B^" _, (C₆F )₄B^", PF₆ ^", BF ^", SbF₆ ^", triflate or p-tosylate group.

26. The compound of claim 15 wherein X represents a BArF^", (C₆F₅)₄B, PF₆ ^", BF₄ ^" or SbF ^" group.

27. The compound of claim 15 wherein at least one L represents a ligand comprising an oxygen, nitrogen, phosphorous or sulfur atom which has a non- bonded electron pair.

28. The compound of claim 27 wherein said ligand includes an ether, amine, phosphine or thioester.

29. The compound of claim 28 wherein said ligand includes THF or pyridene. 75

30. The compound of claim 15 wherein at least one T represents a methyl, ethyl, propyl, butyl, amyl, isoamyl, hexyl, iso-butyl, heptyl, octyl, nonyl, decyl, cetyl, 2-ethylhexyl, or phenyl group.

31. The compound of claim 15 wherein at least one T represents chloro, bromo, fluoro, and iodo group.

32. The compound of claim 15 wherein in at least one T is a chloro group.

33. The compound of claim 15 wherein at least one T represents an alkoxido or an aryloxido group.

34. The compound of claim 15 wherein at least one T independently represents methoxide or ethoxide.

35. The compound of claim 15 wherein a=2.

36. The compound of claim 35 wherein b=2.

37. A process for the polymerization of at least one olefin monomer and/or oligomer, comprising the step of: intimately contacting said at least one monomer and/or oligomer with a catalyst system including: a catalyst compound represented by Formula (I):

76

opάcnally

wherein

R and R' independently represent a hydrogen atom, or a substituted or unsubstituted, branched or unbranched hydrocarbyl or organosilyl radical;

R¹, R² and R³ independently represent a hydrogen atom, or a substituted or unsubstituted, branched or unbranched hydrocarbyl radical; and M is a group DTJB, rVB, VB, VIB, VBB or VDI transition metal;

T independently represents a univalent anionic ligand such as a hydrogen atom, or a substituted or unsubstituted hydrocarbyl, halogeno, aryloxido, arylorganosilyl, alkylorganosilyl, amido, arylamido, phosphido, or arylphosphido group, or two T groups taken together represent an alkylidene or a cyclometallated hydrocarbyl bidentate ligand;

L independently represents a sigma donor stabilizing ligand; X, which is optional, represents a relatively weakly coordinated anion; and a = 0 to 4 inclusive, b = 0 to 4 inclusive, provided a+b < 4; 77

under conditions of temperature and pressure to induce polymerization of said at least one monomer and/or oligomer whereby a polymer product is obtained.

38. The process of claim 37, further comprising the step of: utilizing said catalyst compound along with a metal alkyl co-catalyst.

39. The process of claim 38, wherein said co-catalyst is an alkyl aluminum compound.

40. The process of claim 39, wherein said alkyl aluminum compound includes a trialkylaluminum or an aluminoxane.

41. The process of claim 40, wherein said aluminoxane is selected from the group consisting of ethyl aluminoxane, isobutyl aluminoxane, and methyl aluminoxane.

42. The process of claim 40, wherein said alkyl aluminum compound includes triethylaluminum.

43. The process of claim 37, wherein said contacting step is conducted at a temperature between about -100┬░C to about 200┬░C.

44. The process of claim 37, wherein said contacting step is conducted at a temperature between about 30┬░C to about 135┬░C.

45. The process of claim 37, wherein said contacting step is conducted at pressure between about atmospheric to about 1000 psig.

46. The process of claim 37, wherein said contacting step is conducted at a pressure between about 20 to about 800 psig.

47. A process for making a catalyst comprising the steps of: contacting a compound represented by Formula (III) m

Ri\ R

/

^ΓûáN

R m

-N

\

R2 R'

with a transition metal containing compound to form a catalyst compound represented by Formula (I):

I

optionally

wherein 79

R and R' independently represent a hydrogen atom, or a substituted or unsubstituted, branched or unbranched hydrocarbyl or organosilyl radical;

R¹, R² and R³ independently represent a hydrogen atom, or a substituted or unsubstituted, branched or unbranched hydrocarbyl radical; and

M is a group DTB, rVB, VB, VIB, V1TB or Vm transition metal;

T independently represents a univalent anionic ligand such as a hydrogen atom, or a substituted or unsubstituted hydrocarbyl, halogeno, aryloxido, arylorganosilyl, alkylorganosilyl, amido, arylamido, phosphido, or arylphosphido group, or two T groups taken together represent an alkylidene or a cyclometallated hydrocarbyl bidentate ligand;

L independently represents a sigma donor stabilizing ligand; X, which is optional, represents a relatively weakly coordinated anion; and a = 0 to 4 inclusive, b = 0 to 4 inclusive, provided a+b < 4.

48. The process of claim 47 wherein said transition metal containing compound comprises at least one metal that is equivalent to the transition metal represented by M.

49. The process of claim 48 wherein said metal is a group INB, VB, or VIB transition metal.

50. The catalyst system of claim 49, wherein said transition metal is selected from the group consisting of titanium, vanadium, and chromium.

51. The process of claim 47, wherein said transition metal is a transition metal salt selected from the group consisting of transition metal halide, transition metal carboxylate, transition metal alkoxide and transition metal sulfonate.

52. The process of claim 47, wherein said transition metal is a transition metal halide selected from the group consisting of dichloride metal salt, trichloride metal salt, and tetrachloride metal salt.