CA2321419A1 - 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; R1, 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+b4.

Description

CATALYST COMPOUNDS WTrH BETA-DIIMINATE ANIONIC LIGANDS AND PROCESSES FOR
POLYMERIZING
OLEFINS
FIELD OF THE INVE11'TION
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
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.
2o 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 (3-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) R R
N N -f-~7 ~-a ~b X
\R ~~y \
R
wherein R and R' independently represent a hydrogen atom, or a substituted or unsubstituted, branched or unbranched hydrocarbyl or organosilyl radical;
R', R2, and R3 independently represent a hydrogen atom, or a substituted or unsubstituted, branched or unbranched hydrocarbyl radical; and to M represents a group LIIB, IVB, VB, VIB, VIIB or VIII
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, 15 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 ~3-20 diiminate ligand represented by Formula (TI) (below);
X, which is optional, represents a relatively weakly coordinated anion; and WO 99/41290 PCT/US99/0186_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 5 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 (>] or a heterogeneous catalyst system comprising a Formula (1] catalyst and one or more co-catalysts.
10 The present invention also provides for a novel process of making a catalyst component represented by Formula ()) by contacting a group I>IB, NB, VB, VIB, V1ZB or VIB transition metal containing compound with a compound containing a (3-diiminate ligand represented by the following Formula (II), in particular a compound represented by Formula (>~ (below):

/R

R' WO 99/41290 PCT/US99/0186_3 R

N

' R3 ~

m N

R2 R' wherein 5 R, R', R~, R2 and R~ 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 IIA
metal.
to BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 depicts the crystal structure of the (Ph)2nacnacTiCl2(THF)2, prepared in Example 1 A.
Fig. 2 depicts the crystal structure of the (Ph)2nacnacVCl2(THF)2, prepared in Example 1B.
15 Fig. 3 depicts the crystal structure of the (Ph)2nacnacCrCl2(THF)2, prepared in Example 1C.
Fig. 4 depicts the crystal structure of the (Ph)2nacnacVMe2, prepared in Example 3A.
Fig. 5 depicts the crystal structure of the 20 (Ph)ZnacnacVMe(Et20)(THF)[B(C6H3(CF3)2)a], prepared in Example SA
(BArF anion not depicted).

WO 99/41290 PCT/US99/0186_3 Fig. 6 depicts the crystal structure of the ((Ph)~nacnac)2Cr, prepared in Example 6.
DETAILED DESCRIPTION OF THE INVENTION
5 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).
l0 "group IA, IIA, IIB, IIIA, IBB, IVB, VB, VIB, VIIB or VIII" refers to the metals within the respective group number of the Periodic Table of the Elements (CRC Handbook of Chemistry and Physics, 78'h ed. 1997-1998).
For example, group IVB would include titanium, zirconium, etc. and group VIII 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 a-olefin" refers to an olefin, defined below, wherein R~°
represents a hydrogen atom or an n-alkyl. If not otherwise stated, linear a-olefin as used herein preferably contains 2 to about 12 carbon atoms.
"olefin" refers to a compound of formula CH2=CHR~°, wherein R~°
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, terpolymers, 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 1118, NB, VB, VIB, VIIB or VIII transition metals. If not otherwise stated, transition metals as used herein preferably includes the group IVB, VB, or VIB transition metals.
"unsaturated hydrocarbyl" refers to a hydrocarbyl radical that contains to 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 (3-diiminate bidentate ligand or a catalyst systems comprising at least one such transition metal catalyst with one or more co-catalysts. The (3-diiminate ligand may be represented by Formula (II), as 2o follows:

R

R' __ wherein R, R', R~, R'' 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 (3-diiminate precursor compound corresponding to the (3-diiminate monoanionic ligand, represented by Formula (II). This synthesis reaction is further 1o discussed in the journal articles by S.G. McGeachin Canadian J. of Chem.
v.46, pp.l X03-1912 (1968) and T. Potesil and H. Potesilova, J. of Chromatogr., v.312, pp. 387- 393 ( 1984), the disclosures of which are hereby incorporated by reference. It will be appreciated from this series of transformations that the ~i-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 (II). 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)ZnacnacH).

RNH NR O 1) Et30+BF4- NRH NR'H +

2) R'NH2 \
Base R\N/~~N~R~ R\N~H,.N~R, _MeLi Reaction Scheme 1: Synthesis of (3-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 ~i-diimine compounds and corresponding monoanionic (3-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 to or in situ (i.e., in the vessel in which the polymerization is to take place).
The ~3-diimine compounds of Formula (111), which may serve as precursors for the monoanionic bidentate ligand, represented by Formula (II), can be reacted with a transition metal compound to form a catalyst compound, 15 as represented by Formula (I), that is useful for the polymerization of olefins.
In a preferred form of the (3-diimine compounds of Formula (11T), the hydrogen or metal containing group represented by m includes hydrogen or a group IA
metal, in particular, lithium, sodium or potassium.
2o Useful transition metal containing compounds for forming such catalyst compounds include those which comprise a group IffB, IVB, VB, V1B, VIIB or VIII transition metal having ligands that may be displaced by the monoanionic bidentate ligand derived from the ~3-diimine precursor 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 (>], 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 trichioride being preferred), transition metal carboxylates (such as acetates), transition metal alkoxides (such as methoxides), or transition metal sulfonates (such as triflates or l0 tosylates). Typically, these catalyst may be formed in the presence of a suitable solvent. Suitable solvents include Lewis bases such ethers, thioethers, amines or nitrites with diethylether and tetrahydrofuran being preferred. In addition, a metal alkyl including, in particular, metal alkyls having a group IA, IIA or IIIA metal such as lithium alkyls (such as alkyl methyl lithium, ethyl 15 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 2o comprising the (3-diiminate ligand, such as those represented by Formula (n, can be subsequently reacted with such metal alkyls to form the desired catalyst compound or a compound of Formula ()7 can be reacted in situ and/or in the presence of an olefin to provide a catalyst having the desired activity.
25 With respect to the catalyst compounds represented by Formula (n, above, the relatively weakly coordinated anion X, when present, may be any suitable anion known for this purpose. Suitable anions are often bulky anions, particularly those that deiocalize their negative charge. X, in Formula (n, preferably represents tetrakis [3,5-bis(trifluoromethyl)phenyl)borate (herein WO 99/41290 PCT/US99/Oi86_3 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)4B. 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, 10 benzene, toluene, chlorobenzene, diethyl ether and the like.
The substituent groups represented by R, R', R~, R2 and R~ 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 2o 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 WO 99/41290 PCT/US99/0186_3 il 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-to isopropylphenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 4-methylphenyl, 2,4,6-trimethylphenyl or 2-t-butylphenyl. R', R2, and R~ 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 VIB
15 transition metal, preferably, chromium, vanadium or titanium. These variables defining the preferred forms of the compounds represented by Formula (>7 are equally applicable, when present, to the preferred forms of the (3-diiminate ligand and ~3-diiminate compound represented by Formula (II) & ()~, 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 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 (n can represent any suitable electron donor iigand. 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, to 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 (n, 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 (1) is meant to characterize a mixture of two or more catalytic compounds whereby a and b represent an average of the wand 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, WO 99/41290 PCT/US99/0186_3 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 5 IIA, I)B, IBA and II>B 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, 1o 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 15 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)~ for the cyclic form and R"(R"-Al-O)~ 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 I 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.

WO 99/41290 PCT/tJS99/0186_3 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 to 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 prig. 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, WO 99/41290 PCT/US99/0186_3 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 5 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 to 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 15 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 2o one or more of the following monomers: ethylene, propylene, I-butene, cyclopentene, I-hexene; with ethylene and mixtures of ethylene with propylene and/or I-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.

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-ds (C6DSNH2) was freshly distilled just prior to use.
Trimethylsilylmethyllithium was supplied as a 1.OM solution in pentane and crystallized as a white crystalline solid from solution at -30°C prior to use.
Benzene-d6 (C6D6) and Tetrahydrofuran-d8 (THF-dA) were pre-dried with Na and stored under vacuum over a Na/K alloy prior to use. Pyridine-ds (pyr-ds) and Dichloromethane-d2 (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 tris(tetrahydrofuran) vanadium (VCl3(THF)3) and Trichloro tris(tetrahydrofuran) titanium (TiCI~(THF)3) are prepared from the corresponding metal trichloride (TiCl3 and VCl3, 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 incorporated by reference.

WO 99/41290 PC1'/US99/0186_3 Trichloro tris(tetrahydrofuran) chromium (CrCI~(THF)~) 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 incorporated by reference.
The crystalline oxonium acid [(3,5-(CF3)ZC6H3)4B]~[H(OEt2)2]+ is to synthesized by exposing a solution of Na[(3,5-(CF3)ZC6H3)4B] in ether to HCl and isolating the [(3,5-(CF3)ZC~H3)4B]-[H(OEt2)2J+. This synthesis is discussed in the article by Brookhart, M.; Grant, B.; Volpe, A.F., Organometallics Vol. I I, No. 11, 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.

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 1 B
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 1o corrected for diamagnetism using Pascal constants and the effective magnetic moment (l.leff) was calculated from the expression:
Neer = 2.828 (Txm)'~' where T is the temperature in Kelvin and xm is the molar magnetic susceptibility corrected for diamagnetism.
Preparation of 2-N-Phenylamino-4-N'-Phenylimino-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 surplus 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)ZnacnacH in accordance with the Reaction Scheme 1 (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 I 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-phenylarnino-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-ds for unlabeled aniline.
EXAMPLE lA
Preparation of 2,4-pentane di(N-phenyl)iminato dichloro bis-tetrahydrofuran titanium, (Ph)2nacnacTiCl2(THF)Z and the Corresponding Compound with the Deuterated Ligand, (Ph-ds)2nacnac:
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 TiCl3(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 was isolated by filtration and washed with cold THF several times. After drying under vacuum, 2.92 g (95°lo yield) of (Ph)2nacnacTiCl2(THF)2 as microcrystalline brown compound was isolated.
5 The resulting compounds were analytically tested and the results are shown in Tables lA.l-3. The single crystal X-ray diffraction results are shown in Fig. 1.

TABLE lA.l ANALYTICAL DATA FOR
{Ph)ZnacnacTiCl2(THF)i (Ph-ds)ZnacnacTiCl2(THF)2 ~H 103.1 89.5 11.4 6.25 3.65 3.27 1.61 NMR (6H,6)(lH,b} (2H) (4H) (8H) (2H) (8H) (CDzCIz)e: 27.07 12.79 8.07 3.95 3.31 *** ***
8 (6H) ( (4H) (4H) (2H) m 1 ~H H) NMR
(THF-dg)':
b ( m ~H 108.7685.80 *** *** *** *** ***
NMR (6H) (1H) (THF-dg)':
t m 'H 16.1 15.4 6.1 *** *** *** ***
NMR (4D) (2D) -(THF)': (4D) m IR 3053m 2971 2928m 2876m 1591 1534si - s m 483s KBr :
(cm 1):

1447m 1359s 1290m 1263s 1185w 1066w919m 840s 761m 709s 518w 447w *** ***

IR 2969m 2928m 2890m 2876m 2271 1575m1530m - w KBrb:
(cm ):

1432m 1369vs 1298vs 1250w 1147w lOlsm875m 852m 824w 769w 557m 464w *** ***

Mass 367 [M+ 311.8 Spectrometry: ( - (3.
m/z 100.0) (THF)2] I
(% ) [M+
-CI(THF)z]

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

UV-vis 517 445 (THF) (493.6 (2383.9 ': M'~ M-~
E crri crri i) ) 2.0(std.
dev.

, 294K) Meltin 154 Pt. -Range: 159C

C 2 H N O ! . ~ ::. . '!
TiCI : . .
' Calculated:C 5$.69H N
(% 6.51 5.48 Measured:
%

Sam ie 1 C 56.86H N
5.89 3.77 Sam le 2 C 57.36H N
6.51 5 t adze lvotes: (Applicable for Tables lA-6) t- indicates analytical results for corresponding catalyst prepared using deuterated ligand, (Ph-ds)2nacnac(H).
a - indicates solvent used for NMR measurements.
b - indicates solvent used for IR measurements.
- indicates solvent used for UV-VIS measurements.
Letter designations after the numbers in the IR results provide an indication of the strength of the designated peak: vs = very strong, s = strong, m = medium, and w =
weak.

Table 1.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 l~) Bond Distance (~) Ti-N( 1 ) 2.086(3) C(4)-C(5) 1.366(6) Ti-N(2) 2.088(3) C(5)-C(6) 1.392{5) Ti-O(2) 2.209(3) C(7)-C(9) 1.386(5) Ti-O( 1 ) 2.213(3) C(7)-C(8) 1.513(5) Ti-Ci( 1 2.3888( 10) C(9)-C( 10) 1.415(5}
) Ti-Cl(2) 2.4001 ( 10) C( 10)-C( 11 ) 1.525(5) N( 1 )-C(7) 1.336(4) C( 12)-C( 13) 1.378(6) N( 1 )-C( 1.439(5) C( 12)-C( 17) 1.386(5) 1 ) 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) O( 1 )-C(21 1.440(6) C( I S)-C( 16) 1.354(7) ) O( 1 )-C( I .458(5) C( 16)-C( 17) I .396(6) 18) O(2)-C(22) 1.428(6) C( 18)-C( 19) 1.470(7) O(2)-C(25) 1.475(5) C( 19)-C(20) 1.468(8}

C(1)-C(2) 1.378(5) C(20)-C(21) 1.514(8) C(I)-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 An Ig c (dee.)Bond Angle Angle (deQ.) N( 1 )-Ti-N(2)87.52(12) C(6)-C( 1 )-N( i 19.9(3) 1 ) N(I)-Ti-O(2)176.65(12) C(1)-C(2)-C(3) 120.8(4) N(2)-Ti-O(2)95.73(9) C(4)-C(3)-C(2) 119.4(4) N(1)-Ti-O(1)95.39(10) C(5)-C(4)-C(3) 120.3(4) N(2)-Ti-O(1)175.83(13) C(4)-C(5)-C(6) 120.4(4) O(2)-Ti-O( 81.40( I 1 C( 1 )-C(6)-C(5 120.0(4) 1 ) ) ) N( 1 )-Ti-Cl(192.48(9) N( 1 )-C(7)-C(9) 123.9(3) ) N(2)-Ti-Cl(1)89.35(10) N(1)-C(7)-C(8) 120.6(3) O(2)-Ti-CI(1)88.33(9) C(9)-C(7)-C(8) 115.5(3) O(1)-Ti-Cl(1)87.55(8) C(7)-C(9)-C(10) 127.9(3) N(1)-Ti-Cl(2)91.33(9) N(2)-C(10)-C(9) 124.1(3) N(2)-Ti-CI(2)94.06( 10) N(2)-C( 10)-C( 120.3{3) 11 ) O(2)-Ti-CI(2)87.69(9) C(9)-C(10)-C(11) 115.6(3) O(1)-Ti-C1(2)88.86(8) C(13)-C(12)-C(17)119.4(3) Cl(1)-Ti-Cl(2)175.00(4) C(13)-C(12)-N(2) 119.7(3) C(7)-N( 1 117.1 (3) C( 17)-C( 12)-N(2)120.9(4) )-C( 1 ) C(7)-N(1)-Ti127.4(2) C(12)-C(13)-C(14)120.5(4) C(1)-N(I)-Ti115.3(2) C(15)-C(14)-C(13)119.4(5) C(10)-N(2)-C(12)116.8(3) C(16)-C(IS)-C(14)120.5(4) C(10)-N(2)-Ti127.7(2) C(15)-C(16)-C(17)120.7(4) C(12)-N(2)-Ti115.2(2) C(12)-C(17)-C(16)119.6(4) C(21)-O(1)-C(18)106.5(3) O(1)-C(I8)-C(19) 107.4(4) C(21)-O(1)-Ti126.5(3) C(20)-C(19)-C(18)108.0(4) C(18)-O(1)-Ti126.7(3) C(19)-C(20)-C(21)104.9(5) C(22)-O(2)-C(25)107.1(3) O(1)-C(21)-C(20) 106.4(4) C(22)-O(2)-Ti127.4(3) O(2)-C(22)-C(23) 108.2(5) C(25)-O(2)-Ti 125.2(3) C(22)-C(23)-C(24) 107.1(5) C(2)-C(1)-C(6) 119.1(3) C(23)-C(24)-C(25) 103.2(5) C(2)-C(1)-N(1) 120.9(4) O(2)-C(25)-C(24) 106.0(5) Table 1A.3 Structure Determination Summary for (Ph)2nacnacTiClZ(THF)2 Crystal Data Formula C25H33CI2N2O2T1 Formula Weight S 12.33 Crystal color red to 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) A

a = 90 (3 = 90 y = 90 Volume 2517.8(2) ~3 2o Z 4 Density (calc.) 1.352 g/cm3 Absorption Coefficient 5.76 cm ~

F(000) 1076 Data collection Diffractometer Used Siemens P4 Radiation MoKa (1 = 0.71073A) Temperature 223(2) K

Monochromator Highly oriented graphite crystal 28 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;", = 3.41 %) Observed Reflections 3916 Solution and Refinement System Used SHELXTL (5.03) Solution Direct Methods Refinement Method Full-Matrix Least-Squares Quantity minimized S[w(Fo2 - F~2)2~IS[(WFp2)2~1/2 Hydrogen Atoms idealized contributions Weighting Scheme W ~ = s2(F) + 0.0010 FZ

Final R Indices (obs. data)R = 4. I 5%, wR = 10.51 %

R Indices (all data) R = 5.34%, wR = 11.50%

to Goodness-of-Fit 1.272 Data-to-Parameter Ratio 15.8:1 Largest Difference Peak 0.355 Largest Difference Hole -0.249 Preparation of 2,4-pentane di(N-phenyl)iminato dichloro bis-5 tetrahydrofuran vanadium, (Ph)2nacnacVCl2(THF)2 and the Corresponding Compound with the Deuterated Ligand, (Ph-ds)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 10 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)~ was dissolved in 150 ml of THF. The THF solution of (Ph)2nacnacLi was then 15 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 purple 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 20 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 1B.1-3. The single crystal X-ray diffraction results are shown in Fig. 2.

WO 99/41290 PCT/US99/0186.~

TABLE 1B.1 ANALYTICAL DATA FOR
(Ph)ZnacnacVCl2(THF)2 (Ph-~ds)~nacnacVCh(THF)~
'H NMR (CDZCI2)':111.5299.81 86.72 25-8 8.49 5.55 1.83 8 ( m) (2H,b)(2H,b) (1 (4H,vb) ( ( (8H) H,b) I 11 H) H,b) 'H NMR (THF-dg)':107.5986.92 12.22 6.23 *** *** ***
8 ( m (6H) (IH) (4H) (6H) 'H NMR (THF-da)':108.7685.80 *** ***- *** *** ***
t (6H) (IH) b m 'H NMR (THF)':12.1 6.2 *** *** *** *** ***
$ ( m (4D) (6D) IR - KBr: cni 3053m 3031m 2968s 2927m 2879m 1590m 1532s ) 1485s 1435m 1430m 1368m 1319s 1066w _ 1021s 924s 784w 779m 524w 920m 708s 87Ss 844s IR - KBr: (ctxi2968m 2927m 2876m 2269w 1561 1528vs 1430m ): m 1382vs1318vs 1242m 1021s 924w 870m 8S4m 811w 779w 556m 457m *** *** ***

Mass Spectrometry:369.99 299.04 m/z 9b (37) {32) [M+ [M+
- -(THF)z] CI(THF)z]

Mass Spectrometry:380.02 345.05 t ( (2.54) m/z % 100.0) [M' [M+ -- CI(THF)z]
(THF)z]

UV-vis (THF)':598(1,318.4 474(1,404.2 350(10,57 7~,""x(E) M''crri') M-'crri') 4.7 M' ~cm ~) 3.2(std.
dev.
1), (294K

Meltin Pt. 162 Range: -Cases N O VCI r, :: y ; ,, .
. . :
;
, Calculated: C 58.26 H 6.45 N 5.44 (%) Measured: (%) C 57.81 H 6.37 N 3.77 Table 1B.2 Interatomic Distances and Angles for (Ph)ZnacnacVCl2(THF)Z

(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 (t~) Bond Distance (~) V(I)-N(1) 2.023(2) C(6)-C(11) 1.382(4) V(1 )-N(2).2.030(2) C(7)-C(8) 1.379(S) V( I )-O( 2.208(2) C(8)-C(9) 1.366(S) 1 ) V(1)-O(2) 2.221(2) C(9)-C(10) 1.393(4) V ( I )-CI(2.3592(6) C( 10)-C( I 1 1.389(3) 1 ) ) V( I )-Cl(2)2.3646(6) C( 12)-C( 13) 1.383(4) O( I )-C(211.445(4) C( 12)-C( 17) 1.385(4) ) O(1)-C(18) 1.456(4) C(13)-C(14) 1.397(4) O(2)-C(2S) 1.447(4) C(14)-C(IS) 1.382(4) O(2)-C(22) 1.480(4) C( 1 S)-C( 16) 1.386(4) N( 1 )-C( 1.345(3) C( 16)-C( 17) 1.393(4) I ) N( I )-C( 1.430(3) C( 18 )-C( 19) 1.506(5 11 ) ) N(2)-C(3) 1.337(3) C(19)-C(20) 1.471(6) N(2)-C( 1.431 (3) C(20)-C(21 ) 1.488(5) 17) C(I)-C(2) 1.400(3) C(22)-C(23) 1.518(S) C( 1 )-C(4)I.S23(4) C(23)-C(24') 1.39(2) C(2)-C{3) I .395(4) C(23)-C(24) 1.SS9(13) C(3)-C(S) 1.509(3) C(24)-C(2S) 1.383( 10) C(6)-C(7) 1.380(4) C(24')-C(25) 1.597(12) Bond Anele An~le (dee.) Bond Anele An~le (dee.) N(1)-V(1)-N(2)90.94(9) N(2)-C(3)-C(2) 123.5(2) N(1)-V(1)-O(2)94.15(7) N(2)-C(3)-C(S) 120.6(2) N(2)-V(I)-O(2)174.89(9) C(2)-C(3)-C(S) 115.8(2) N(1)-V(1)-O(1)174.75(9) C(7)-C(6)-C(11) 120.9(3) N(2)-V(1)-O(1)93.45(7) C(8)-C(7)-C(6) 120.0(3) O(2)-V(I)-O(1)81.44(8) C(9)-C(8)-C(7) 119.8(3) N(1)-V(1)-Cl(I)89.68(7) C(8)-C(9)-C(10) 120.?(3) N(2)-V(1)-CI(1)91.35(7) C(I1)-C(10)-C(9) 119.7(3) O(2)-V(1)-CI(1)88.24(7) C(6)-C(11)-C(10) 118.9(3) O(1)-V(1)-Cl(I)87.33(6) C(6)-C(11)-N(1) 120.2(2) N(1)-V(1)-Cl(2)93.78(7) C(10)-C(I1)-N(1) 120.8(2) N(2)-V(1)-CI(2)92.22(7) C(13)-C(12)-C(17)121.0(3) O(2)-V ( 87.90(7) C( 12)-C( 13)-C( 119.6(3) 1 )-Cl(2) 14) O(I)-V(1)-CI(2)88.93(6) C(1S)-C(14)-C(13)119,8(3) Cl(I)-V(1)-CI(2)174.99(3) C(14)-C(IS)-C(16)120.2(3) C(21)-O(I)-C(18)106.5(2) C(15)-C(16)-C(17)120.4(3) C(21)-O(1)-V(1)126.8(2) C(12)-C(17)-C(16)119.0(3) C(18)-O(1)-V(1)125.8(2) C(12)-C(17)-N(2) 120.3(2) C(25)-O(2)-C(22)108.2(3) C( 16)-C( 17)-N(2)120.7(2) C(2S)-O(2)-V(126.5(2) O( 1 )-C( 18)-C(19)l OS.9(3) 1 ) C(22)-O(2)-V(1)125.0(2) C(20)-C(19)-C(18)106.0(3) C(1)-N(1)-C(I1)116.4(2) C(19)-C(20)-C(21)107.0(3) C(1)-N(1)-V(1)126.2(2) O(1)-C(21)-C(20) 107.2(3) C( I 1 )-N(117.1 (2) O(2)-C(22)-C(23) 104.8(3) 1 )-V( 1 ) C(3)-N(2)-C(17)117.6(2) C(24')-C(23)-C(22)102.0(7) C(3)-N(2)-V(1)125.8(2) C(22)-C(23)-C(24)105.5(5) C(17)-N(2)-V(116.4(2) C(25)-C(24)-C(23)106.9(7) 1 ) N(1)-C(1)-C(2)123.3(2) C(23)-C(24')-C(25)104.7(6) N(1)-C(1)-C(4)120.3(2) C(24)-C(25)-O(2) 110.7(S) C(2)-C(1)-C(4)116.4(2) O(2)-C(25)-C(24')102.3(7) C(3)-C(2)-C(I)128.8(2) WO 99/41290 PCT/US99/0186_3 Table 1B.3 Structure Determination Summary for (Ph)=nacnacVCh(THF)Z
Crystal Data Formula C2SH33Cl2N2O2V

Formula weight 515.37 Crystal color black block Crystal Size (mm) 0.35 x 0.25 x 0.14 Crystal System orthorhombic 1o Space Group Pna2, Unit Cell Dimensions a = 19.5215(4) A

b = 9.5341 (2) A

c = 13.4898(3) A

a = 90 t5 ~i = 90 y = 90 Volume 2510.72(9) A

Density {calc.) 1.363 g/cm~

2o Absorption Coefficient 6.32 cm~i F(000) Data collection Diffractometer Siemens P4 25 Radiation MoKa (1 = 0.71073A) Temperature 218(2) K

Monochromator Highly oriented graphite crystal 28 Range (w) 4.18 to 56.56 30 Scan type Omega, Phi Scan Range 0.3 Index Ranges -25 <h < 12 -10<k< 12 -17 < 1 < 17 35 Reflections Collected 9021 Independent Reflections 5585 (R;"~ = 2.04%) Observed Reflections 4948 Solution and Refinement System Used SHELXTL (5.03) Solution Direct Methods Refinement Method Full-Matrix Least-Squares Quantity minimized S[w(Fo2 - F~2)2]/S[(wFo2)2~u'-Hydrogen Atoms Idealized contributions Weighting Scheme w-~ = 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 Preparation of 2,4-pentane di(N-phenyl)iminato dichloro bis-5 tetrahydrofuran chromium, (Ph)2nacnacCrCl2(THF)2 and the Corresponding Compound with the Deuterated Ligand, (Ph-ds)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 10 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)~ 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
15 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 2o shown in Tables 1 C.1-3. The single crystal X-ray diffraction results are shown in Fig. 3.

TABLE 1C.1 ANALYTICAL DATA FOR
(Ph)2nacnacCrCl2(THF)2 (Ph-ds)2nacnacCrCl2(THF)Z
'H NMR (CD~CIz)a:111.5299.81 86.72 25-8 8.49 5.55 1.83 8 ( m) (2H,b)(2H,b) (lH,b) (4H,vb) (1H) (llH,b) (8H) 'H NMR (THF-d8)15.46 6.19 12.22 6.23 *** *** ***
: (6H) (4H) (4H) (6H) b ( m) 'H NMR (THF) 16.1 15.4 6.1 *** *** *** ***
a: (4D) (2D) (4D) t 8 ( m) IR - KBrb: 3050w 3017m 2966s 2928s 2883s1590w 155Svs (cm ):

1530vs1484vs 1448vs 1387vs 1263s1200s1065 1017s w 921m 871m 848s 764m 710s 662w 526m 477w IR - KBr : 2967m 2926m 2878m 2269w1550m1528vs 1453m (cm-'):
t 1381vs 1320vs 1157m 1016m969m 869m 855m 811w 753m 558m 427m *** *** ***

UV-vis (THF)':598(1,318.4 474(1,404.2 350(10,574.7 ax(E) M~'crri') M- M-cm cni ) ) Mass Spectrometry:370.76 335.81 300.86(6.01 m/z (%) (41.24) (41.60) ) [M+ M+ [M+
- - -(THF) CI(THF Clz(THF) ) Mass Spectrometry:381.02 346.05(46.83) 311.09(5.45) t m/z (%) ( [M+ [M+
19.41 - -) CI(THF Clz(THF) [M+ ] ]
-(THF)z]

UV-vis (THF)':527(572.2 419(8,232.5 400(5,711.7 ~az(E) M''crri M~ M-'cni') ~) cm ) 4.1(std.
dev.
1), ~
(294K) Melting Pt. 174 Range: -CzSH 3N OzCrCI

Calculated: C: J2S.14 H 6.44 N 5.42 (%) Measured: (%) C 57.95 H b.81 N 5.51 Table 1C.2 Interatomic Distances and Angles for (Ph)znacnacCrCl2(TIiF) (Note: the bond designations are with reference to FIG.
3 and the values noted in parentheses after the eviation.) distances and angles represent the estimated standard d Bond Distance (A) Bond Distance (A) Cr(1 )-N( 2.032(6) C(6)-C(7) 1.398(7) 1 ) Cr( 1 )-N(2)2.033(5) C(7)-C(8) 1.415(8) Cr( 1 )-O(2)2.141 (5) C(8)-C(9) 1.347(9) Cr( 1 )-O( 2.144(5 ) C(9)-C( 10) 1.402(8) I ) Cr( 1 )-Cl(2.3392( 12) C( 10)-C( I 1 1.415(7) 1 ) ) Cr( 1 )-Cl(2)2.3532( 12) C( 12)-C( 17 1.369(7) ) O( 1 )-C(18)1.462(8) C( 12)-C( 13) 1.406(8) O(1)-C(21) 1.464(8) C(13)-C(14) 1.383(8) O(2)-C(2S) 1.459(8) C(14)-C(15) 1.393(8) O(2)-C(22) 1.473(8) C(IS)-C(16) 1.374(8) N( 1 )-C( 1.31 S(8) C( 16)-C( 17) 1.424(7) 1 ) N(1)-C(11) 1.459(7) C(18)-C(19) 1.526(9) N(2)-C(3) 1.323(8) C(19)-C(20) 1.519(11) N(2)-C(17) 1.453(7) C(20)-C(21) 1.492(10) C( 1 )-C(2)I .431 (7) C(22)-C(23 ) 1.497( I
0) C(1)-C(4) 1.537(8) C(23)-C(24') 1.40(3) C(2)-C(3) 1.412(8) C(23)-C(24) 1.58(2) C(3)-C(5) 1.525(8) C(24)-C(25) 1.47(2) C(6)-C(11) 1.377(8) C(24')-C(25) 1.50(3) Bond Anele An Ig_e (dee Bond Angle Anale (den.) ) N( 1 )-Cr(191.7(2) N(2)-C(3)-C(2) 124.7(5) )-N(2) N( 1 )-Cr( 93.4(2) N(2)-C(3)-C(5) I 21.2(6) 1 )-O(2) N(2)-Cr(1)-O(2)174.8(2) C(2)-C(3)-C(5) 114.1(6) N( 1 )-Cr( 176.0{2) C( 11 )-C(6)-C(7)I 21.7(5) 1 )-O( 1 ) N(2)-Cr(1)-O(1)92.1(2) C(6)-C(7)-C(8) 118.0(5) O(2)-Cr(I)-O(1)82.7(2) C(9)-C(8)-C(7) 120.5(6) N(1)-Cr(I)-Cl(1)88.5(2) C(8)-C(9)-C(10) 122.2(6) N(2)-Cr(I)-Cl(1)89.5(2) C(9)-C(10)-C(11)118.0(6) O(2)-Cr( 90.1 (2) C(6)-C( 1 I )-C(1 19.6(5) I )-Cl( 10) 1 ) O(1)-Cr(I)-CI(1)90.28(13) C(6)-C(II)-N(I) 121.1(5) N(1)-Cr(1)-Cl(2)90.6(2) C(10)-C(11)-N(1)119.1(5) N(2)-Cr(1)-Cl(2)90.1(2) C(17)-C(12)-C(13)120.8{S) O(2)-Cr(1)-Cl(2)90.3(2) C(14)-C(13)-C(12)119.8(5) O(1)-Cr(1)-Cl(2)90.71(13) C(13)-C(14)-C(15)119.5(6) Cl(1)-Cr(1)-C1(2)178.95(11) C(16)-C(15)-C(14)121.3(5) C(l8)-O(1)-C(2l)106.3(6) C(15)-C(16)-C(17)119.3{5) C(18)-O(1)-Cr(1)126.5(4) C(12)-C(17)-C(16)119.3(5) C(21)-O(1)-Cr(1)125.8(4) C(12)-C(17)-N(2)121.6(5) C(25)-O(2)-C(22)107.4(6) C(16)-C(17)-N(2)119.0(5) C(25)-O(2)-Cr(1)126.9(4) O(1)-C(18)-C(19)105.9(6) C(22)-O(2)-Cr(I)125.2(5) C(20)-C(19)-C(18)103.8(6) C(1)-N(1)-C(ll)117.1(5) C(21)-C(20)-C(19)107.4(6) C( 1 )-N( 125.7(4) O( I )-C(21 )-C(20)106.8(6) 1 )-Cr( 1 ) C(I1)-N(1)-Cr(I)116.8(4) O(2)-C(22)-C(23)105.8(7) C(3)-N(2)-C(17)117.7(5) C(24')-C(23)-C(22)100.4(12) C(3)-N(2)-Cr(1)125.3(4) C(22)-C(23)-C(24)109.4(9) C(17)-N(2)-Cr(1)117.0(4) C(25)-C(24)-C(23)101.3(13) N(1)-C(1)-C(2)124.6(6) C(23)-C(24')-C(25)109(2) N(I)-C(I)-C(4)121.2(5) C(24)-C(25)-O(2)112.3(10) C(2)-C(1)-C(4)114.2(6) O(2)-C(25)-C(24')103(2) C(3)-C(2)-C(1)126.9(6) Table 1C.3 Structure Determination Summary for (Ph)ZnacnacCrCl2(THF) Crystal Data Empirical Formula Cz5H33C12N202Cr 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) t~

b = 9.597 I (2) ~

c = 13.4509(3) ~

a = 90 (3=90 t 5 'y = 90 Volume 2533.00(9) A3 Formula Weight S 16.43 Density (calc.) 1.354 g/cm~

Absorption Coefficient 6.87 cm's F(000) 1084 Data collection Diffractometer Used Siemens P4/CCD

Radiation MoKa {I = 0.71073A) Temperature 218(2) K

Monochromator Highly oriented graphite crystal 28 Range (w) 4.16 to 56.12 3o 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;"t = 13.02%) Observed Reflections 2408 WO 99/41290 PCT/1.JS99/01863 3a Solution and Refinement System Used SHELXTL (5.03) Solution Direct Methods Refinement Method Full-Matrix Least-Squares s Quantity minimized S[w(Fo2 -F~2)2]/S [(wFo2)2) iiz Hydrogen Atoms Idealized contributions Weighting Scheme w-~ = s2(F) + 0.0010 F2 Final R Indices (obs. data) R = 5.35%, wR = 11.14%

to R Indices (all data) R =10.56%, wR = 16.45%

Goodness-of-Fit 0.808 Data-to-Parameter Ratio 14.2: I

Largest Difference Peak 0.375 Largest Difference Hole -0.880 Preparation of 2,4-pentane di(N-phenyl)iminato chloro methyl vanadium, (Ph)2nacnacV(Cl)(Me):
0.97 mmoles (0.500 g) of (Ph)2nacnacVCl2(THF)2, reference Example 1B, 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 LiCI.
The ether solution was concentrated and cooled to -30°C for crystallization. A
microcrystalline brown powder was filtered and washed with cold pentane.
3o 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.

ANALYTICAL DATA FOR
(Ph),nacnacV(CIl(Mel ~H NMR (C6D6)a:8.70 -3.90 *** *** *** *** ***
8 ( m) (6H,vb)(2H,vb) IR - KBrb: 3057w 3029w2992w 2959w 2918w 2848wI592m (cm- ) 1530s 1510m1483s 1447m 1427m 1371s1339s 1299m 1262m1184w 1071w 1023m 1023s997m 937w 918w 854w 799w 754s 700s SlSm Mass Spectrometry:350 335( 299(6) m/z (%) ( I 100) [M' S) [M+ -M'" - CH~CL]
CH
]

UV-vis (Et20)541 435 ': (4.27x ( x(e) 10 I
M-~ .42x crri 10 ~ ) M'' cm ) ff 3.0(std.
dev.
1 ), B (294K) Melting Pt. 132 Range: - 134C

Calculated: I C: 61.64 I H J. /J I N -/.yy I I 1.:
Measured: (%) ~ C 61.53 ~ H 5.74 ~ N 7.98 ~ ~ ~ ]

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)ZnacnacVCl2(THF)2, reference Example 1B, 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 1o 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 LiCI. 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)~ crystals were isolated after two crystallization extraction cycles. The crystals were analytically tested 2o and the results are shown in Table 2B.

ANALYTICAL DATA FOR
s (Ph)2nacnacV(CI)(CHzSi(CH;)s) 'H NMR (C6D6)a:8.69 -1.40 3.16 *** *** *** ***
b ( m) (6H) (9H) (2H) IR - KBr : 30s6w 3026w (cm- ) 2999w 29s6m 2922m 28sOw 1593m 1532s 1510m 1485s1447m 1431m 1371vs 1299m 1251m 1071 1022m 998m848s 757m 701 488w 471 w s w Mass Spectrometry:422(7) 335(57) m/z (%) [M+] [M+-CHZSi(CH3)sl LJV-vis (Et20)':s41 629 az(~) (266 (421 M~' M'' cm'') crri') 3.0(std.
dev.
1 ), (294K) Melting Pt. 2s0-2s4C
Range:

CZ,H gN CIVSi 1o Preparation of 2,4-pentane di{N-phenyl)iminato dimethyl vanadium, {Ph)2nacnacVMe2:

5.0 mmoles (2.58g,) of (Ph)2nacnacVCl2(THF)2, reference Example 1 B, was suspended in 150m1 of THF and cooled to -30°. 11.0 mmoles (2.2 15 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 LiCI. The solution was concentrated to 30 2o 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(CI)(Me) were isolated after vacuum drying. The content of the chloride impurity ranges from 18 to 50%.

WO 99/41290 PCT/US99/018b3 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
(Phl~nacnacVMe~
~H NMR (C6D6)':8.68 -4.99 *** *** *** *** ***

8 m) (6H) (2H) IR - KBr : 3053m 3031m 2968s 2927m 2879m 1590m 1532s (crri ~) 1485s 1435m 1430m 1368m 1319s 1066w 1021s 924w 784w 779m 708s 920m 524w 875s 844s Mass Spectrometry:330 315(22.29) 300(29.24) (23.4) m/z (lo [M+] [M+ [M+
- -CHI] 2CH~]

UV-vis (Et20) 597 446 '~: (194.4 (334 M-~ M-cm's) cm' ) ~nax(E) 3.1(std.
dev.
1), B
(294K) Meliir~g Pt. 125-129C
Rangc:

C,aHasN 'J .. .:' : .. ;: ....
. ' . .
.:: ..

~aicmaieo: ~ ion l: O%.U2S ri /.UL. N tS.4tS
Measured: (%) C 64.?6 H 6.36 N 8.29 Table 3A.2 Interatomic Distances and Angles for (Ph)ZnacnacVMe2 (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 ltd) Bond Distance (A) V-N( 1 ) 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(1) 2.080(4) C(8)-C(9) 1.387(6) V-C 2.126(4) C(9)-C(10) 1.385(7) N( 1 )-C(2)1.353(5 ) C( 10)-C{ 11 ) 1.396(6) N( 1 )-C( 1.448(5) C( 11 )-C(12) 1.378(6) 12) N(2)-C(4) I .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(IS)-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 Anr~leAngle (dee.) Bond Angle An~le (dee.) N(1)-V-N(2)92.11(13) C(3)-C(4)-C(6) 117.6(3) N( 1 )-V-C(11 I .1 (2) C(8)-C(7)-C( 12) 120.0(4) 1 ) N(2)-V-C(1)115.1(2) C(9)-C(8)-C(7) 120.4(4) N(1)-V-C 114.72(14) C(10)-C(9)-C(8) 119.4(4) N(2)-V-C 108.4(2) C(9)-C(10)-C(11) 120.5(4) C(1)-V-C II3.6(2) C(12)-C(11)-C(10)120.9(4) C(2)-N(1)-C(12)120.4(3) C(11)-C(12)-C(7) 118.6(4) C{2)-N(I)-V127.6(3) C(II)-C(12)-N(1) 123.5(4) C(12)-N(1)-V111.8(2) C(7)-C(12)-N(1) 117.6(3) C(4)-N(2)-C(18)119.2(3) C(18)-C(13)-C(14)119.6(4) C(4)-N(2)-V127.2(3) C(15)-C(14)-C(13)119.7(4) C(18)-N(2)-V113.5(2) C(14)-C(15)-C(16)120.3(4) N(1)-C(2)-C(3)122.0(3) C(15)-C(16)-C(17)120.4(5) N(I)-C(2)-C(5)120.9(3) C(18)-C(17)-C(16)119.9(4) C(3)-C(2)-C(5)117.1(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)119.4(3) Table 3A.3 Structure Determination Summary for (Ph)ZnacnacVMe~
Crystal Data Formula C,9H23N2V

Formula weight 330.13 5 Crystal color brown block Crystal Size (mm) 0.40 x 0.20 x 0.10 Crystal System monoclinic Space Group P2i/n Unit Cell Dimensions a = 8.6616(2) ~r to b = 15.9937(4) A

c = 13.2812(1) A

a = 90 (3 = 93.317(2) 'y = 90 15 Volume 1836.78(8) /~;

Density (calc.) 1.220 g/cm~

Absorption Coefficient 6.05 cm F(000) Data collection Diffraetometer Siemens P4 Radiation MoKa (1= 0.71073.) Temperature 295(2) K

Monoehromator Highly oriented graphite crystal 29 Range (w) 3.98 to 56.30 Scan type Omega, Phi Scan Range 0.3 3o Index Ranges -11 <h < 10 18<k<21 -17 < 1 < 16 Reflections Collected 7272 Independent Reflections 3894 (R;"~ = 4.00%) Observed Reflections Solution and Refinement System Used Siemens SHELXTL (5.03) Solution Direct Methods Refinement Method Full-Matrix Least-Squares s Quantity minimized S[w(F~2 - F~Z)2]/S[(wF
2)2]1/2 Hydrogen Atoms Idealized contributions Weighting Scheme w-~ = s2(F) + 0.0010 Final R Indices (obs. R =6.01 %, wR = 15.52%
data) 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 WO 99/41290 PCT/US99I0186.~

Preparation of 2,4-pentane di(N-phenyl)iminato bis-trimethyl silylmethyl vanadium, (Ph)ZnacnacV(CHZSi(CH3)3)z:
1.94 mmoles ( 1.00 g) of (Ph)ZnacnacVCl2(THF)2, reference Example 1B, 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
to 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 LiCI. 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)Z, was isolated by evaporation of the solvent. The oil was analyzed and the results are shown in Table 3B.

ANALYTICAL DATA FOR
(PhhnacnacVlCH~Si(CH~)z)~
'H NMR (CbDb): 8.56 -0.92 -3.69 *** *** *** ***
b ( m (6H) (i8H) (2H) IR - neat : 306iw 3031w 2816w 1592m cm' 2948s 2889m 2862w 1528s 1510s 1483vs 1447s1429m 1362vs 1262m1241s 1184w 1069w 1025m 935w884vs 845vs 750s 700vs Mass Spectrometry:474.32(4.1 386.22(58.47) 300(24.56) m/z ) [M+- [M+-(%) [M''] SiMe4] 2CH2Si(CH3)sl Preparation of 2,4-pentane di(N-phenyl)iminato (OTf)Z bis-tetrahydrofuran vanadium, (Ph)ZnacnacV(OTf)2(THF)Z
0.52 mmoles {270 mg,)(Ph)2nacnacVCl2(THF)2, reference Example 1B, 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 AgCI. 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.

ANALYTICAL DATA FOR
(Ph)znacnacV(OTf)2(THF)2 ~H NMR (THF-dg)126.94 15.91 3.28 *** *** *** ***
a: (6h,vb)(4H,vb)(4H) 8 ( m) IR - KBr : 3061w 3031w 2985w 2933w 2907w 1592w1540m (ctri ) 1487s 1447w 1434w 1339vs 1236vs 1201vs1014s 928w 850m 844s 764w 710m 632s 524w Mass Spectrometry:597.98(6.4) 465.02(54.3) m/z (%) [M' M+
- 2THF] -SOZCF,,2THF) UV-vis (THF)':598(1,318.4 474(1,404.2 350(10,574.7 ax(E) M-~crti M-~crri M-~cm-~) ~) ~) rr 3.2(std.
dev.
1), B (294K) Melting Pt. 160 Range: - 163C

Cz~H33N O
F S V

Calculated: C 43.66 H 4.48 N 3.77 (%) ~. '~ '' Measured: (%) C 42.53 H4.59 N3.87 Preparation of 2,4-pentane di(N-phenyl)iminato methyl diethylether s tetrahydrofuran vanadium tetrakis-(3,5-bis-trifluoromethyl-phenyl)borate, [(Ph)2nacnacVMe(Et20)(THF)][B(C6H3(CF3)2)al~
0.30 mmoles ( 100 mg) (Ph)2nacnacVMe2, reference Example 3A, was dissolved in 20 ml of diethylether and cooled to -30°C. In a separate flask, .30 to mmoles (310 mg) of H(Et20)2[B(C6H3(CF3)2)al 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 °lo yield) of orange ts [(Ph)2nacnacVMe(Et20)(THF)][B(C6H3(CF3)2)a) 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 SA.1-3. The single crystal X-ray diffraction results are shown 2o in Fig. 5.
TABLE SA.1 ANALYTICAL DATA FOR
25 ffPh)2nacnacVMe(Et20)(THF)1(B(C~H3(CF3)2)al ~H NMR (CDZC12)121.4 90.5 8.68 7.73 7.57 0.90 -2.46 : (6H,vb)(lH,vb) (4H,vb) (8H) (4H) (8H,b) (2H,vb) 8( m IR - KBr : 3087w 2982w 2936w 2907w 1610w ISSSm 1486m (cni 1450w 1429w 1356vs 1284vs 1158vs, b 1020m 1133vs,b 938s 897s 795w 758w 710s 700s 679s 670s 525w 496w *** *** *** ***

LTV-vis (EtzO)739(222 609(334 475( ': M crri M' 1350 ax{) ) cm' M' ) cm-) 3.4(std.
dev.
I), B {294K

Melting Pt. 95-97C
Ran e:

CsaHsoN O F
qVB

Calculated: (%) C 53.02 H 3.84 N 2.13 Measured: (%) C 49.89 H 3.28 N 2.16 Table SA.2 Interatomic Distances and Angles for the Cation of [(Ph)znacnacVMe(EtzO)(THF)][B(C6H3(CF3)z)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 (~) Bond Distance (~) V-N(2) 1.94(2) C(8)-C(9) 1.39(4) V-N( 1 ) 2.00(2) C( 10)-C( 11 ) I .38(3) V-O( I ) 2.029( I 3) C( 10)-C( 14) I .50(3) V-C(1) 2.09(2) C(ll)-C(12) 1.53(3) V-O(2) 2.16(2) C( 12)-C( I 3) 1.54(3) O(1)-C(4) 1.45(3) C(15)-C(16) 1.44(3) O( 1 )-C(3) 1.49(3) C( 15)-C(20) 1.37(3) O(2)-C(6) 1.42(3) C( 16)-C( 17) I .37(3) O(2)-C(9) 1.41 (2) C( 17)-C( 18) 1.32(3) N(1)-C(I2} 1.26(3) C(18)-C(19) 1.49(3) N( 1 )-C(20)1.46(2) C(I9)-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) I .64(5) c(2s)-c(26) 1.50(2) Bond Anele An lg a (deg;}Bond An~le An le (dee.) N(2)-V-N( 89.1 (6) C(6)-C(7)-C(8) 97(2) 1 ) N(2)-V-O(1) 134.4(6) C(9)-C(8)-C(7) 106(2) N(I)-V-O(I) 89.6(6) C(8)-C(9)-O(2) 110(2) N(2)-V-C(I) 95.7(10) N(2)-C(10)-C(11) 120(2) N(1)-V-C(I) 91.9(9) N(2)-C(10)-C(14) 119(2) O(I)-V-C(1) 129.9(10) C(11)-C(10)-C(14)120(2) N(2)-V-O(2) 98.0(6) C(10)-C(11)-C(12)129(2) N(1)-V-O{2) 171.0{6) N(1)-C(12)-C(13) 126(2) O( 1 )-V-O(2)81.4(5) N( 1 )-C( I 2)-C(116(2) 11 ) C(1)-V-O(2) 92.9(9) C(13)-C(12)-C(11)117(2) C(4)-O(1)-C(3)109(2) C(16)-C(15)-C(20)118(3) C(4)-O(1)-V 118.3(13) C(17)-C(16)-C(IS)123(2) C(3)-O(1)-V 131(2) C(16)-C(17)-C(18)122(2) C(6)-O(2)-C(9)105(2) C(19)-C(18)-C(17)118(2) C(6)-O(2)-V 122.7(12) C(18)-C(19)-C(20)119(2) C(9)-O(2)-V 132.3(13) C(19)-C(20)-C(15)120(2) C(12)-N(1)-C(20)111(2) C(19)-C(20)-N(1) 119(2) C(12)-N(1)-V132(2) C(15)-C(20)-N(1) 121(2) C(20)-N(1)-V116.4(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)-V131.3(14) C(22)-C(23)-C(24)119(2) C(26)-N(2)-V116.0(11) C(25)-C(24)-C(23)125(2) O(1)-C(3)-C(2)106(2) C(26)-C(25)-C(24)120(2) C(5)-C(4)-O(1)128(3) C(25)-C(26)-C(21)115(2) C(7)-C(6)-O(2)117(2) C(25)-C(26)-N(2) 126.0(14) C(21)-C(26)-N(2) 119(2) WO 99/41290 PCT/US99/0186_3 Tabte SA.3 Structure Determination Summary for [(Ph)ZnacnacVMe(Et20)(THF)J[B(C6H3(CF3)a)41 Crystal Data Formula CsaHsoBFz4N2O2V

Formula Weight 1324.75 Crystal color Orange-brown block Crystal Size (mm) 0.05 x 0.20 x 0.40 l0 Crystal System monoclinic Space Group Cc Unit Cell Dimensions a = 20.1893(11) ~

b = 15.6580( 11 ) ~A

c = 20.1295(13) ~

a = 90 (3 = 106.893(2) y = 90 Volume 6088.8(7) A

Density (calc.) 1.445 g/cm3 Absorption Coefficient 2.79 cm ~

F(000) 2688 Data collection Diffractometer Siemens P4 Radiation MoKa (1= 0.71073A) Temperature 293(2) K

Monochromator Highly oriented graphite crystal 3o 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;"~ = 10.94%) Observed Reflections 4631 WO 99/41290 PCT/US99/0186_3_ Solution and Refinement System Used SHELXTL (5.03) Solution Direct Methods Refinement Method Full-Matrix Least-Squares Quantity minimized S[w(Foz - F~2)2~IS[(WFp2)2]1/2 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 11.1:1 Largest Difference Peak 2.565 Largest Difference Hole -0.531 WO 99/41290 PCT/US99/0186_3 EXAMPLE SB
Preparation of 2,4-pentane di(N-phenyl)iminato methyl bis-diethylether vanadium tetrakis-(3,5-bistrifluoromethylphenyl)borate, [(Ph)ZnacnacVMe(Et20)2][B(C6H3(CF3)i)a]:
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 SA were followed for the synthesis of (Ph)2nacnacVMe(Et20)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 SB the product is believed to contain [(Ph)ZnacnacVMe(Et20)2][B(C6H3(CF3)2)4].

f (Phl~nacnacVMelFt.,Wl.,lfRl('WT..II'F..1_1.7 'H NMR (C6D6)123.95 7.60 4.39 -16.75' ***. *** ***
e: ' ' b ( m) (6H,vb)(4H) (6H) (lH,vb) IR- KBr : 3081w 2977w2936w 2907w 2882w 1610w 1437w (cm' ) 1355vs 1279vsI126m 1027w 945w 887m 839m 798w 771w 744w 713m 682m 448w ***

UV-vis (Et20)':776(266 629(421 M' 469(1400 M~'crri') ctrl M~'crri ) ) a"~ax(E) rr 3.1(std.
dev.
I), B (294K) Melting Pt. 89-93C
Range:

CsH NOF4VB ;r ~.aicmaiea: io ~: ~~.4ts n 3.y~ N 2.! 1 Measured: (% C 49.41 H 3.47 N 2.11 Preparation of bis-( 2,4-pentane di(N-phenyl)iminato) chromium(II), ((Ph)Znacnac)zCr:
Preparation 1: Reaction of 2-N-phenylamino-4-N'-phenylimino-3-pentenyl dichloro bis-tetrahydrofuran chromium, (Ph)~nacnacCrCl2(THF)2, with MeLi:
l0 1.16 mmoles (600 mg) of (Ph)2nacnacCrCh(THF)2, reference Example 1C, 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 1S solution was evaporated to dryness. THF was removed by trituration in ether.
The resulting solid was extracted with ether and filtered to remove LiCI. The black-green filtrate was then concentrated and cooled to -30°C for crystallization. 210 mg (35% yield) of ((Ph)Znacnac)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)2nacnacLi 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 LiCI. 7.09 mmoles (3.7 g, 84% yield) of black ((Ph)Znacnac)~Cr crystals were isolated from a concentrated diethylether solution that was cooled to -30°C.
TABLE 6.1 ANALYTICAL DATA FOR
((Ph)Znacnac)2Cr 'H NMR (C6D6)a:123.957.60 4.39 -16.75 *** *** ***
8 ( m (6H,vb)(4H) (6H) ( H,vb) IR - KBr : 3055w 3029w 2922w 2879m1591w 1540s 1515m ctti ~) 1482s 1449m 1382vs 1276w1264w 1021 866w m 842w 752w 700m *** *** *** ***

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

~H
N

UV-vis (EtzO)':348(shoulder) ***
7,,",a"(E) (10,444.5 M~~crri ~) 5.1 (std.
dev.

, ,~
(294K) Meltin Point: 220C

C14H 4N4Cr Calculated: % C 74.15 H 6.23 N 10.18 Measured: (%) C 72.42 H 6.30 N 10.01 Table 6.2 Interatomic Distances and Angles for ((Ph)Znacnac)ZCr (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( 1 ) 2.058(3) C( 13)-C( 14) I .375(9) Cr-N(4) 2.069(3) C( 14)-C( I S) 1.353(9) N(1)-C(2) 1.336(5) C(15)-C(16) 1.392(7) N(l)-C(11) 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(1)-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( 11 ) 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(31 )-C(32) 1.387(7) C(9)-C(10) 1.378(7) C(32)-C(33) 1.383(7) C( 10)-C( 1 I l .380(6) C(33)-C(34) 1.398(6) ) Bond Anele An Ig a (dee.)Bond Angle An Ig-a (deQ.) N(2)-Cr-N(3) 149.78(14) C(10)-C(11)-N(1)121.3(4) N(2)-Cr-N(1) 88.47(14) C(17)-C(12)-C(13)120.0(5) N(3)-Cr-N(1) 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)119.7(5) N(3)-Cr-N(4) 89.35(14) C(14)-C(15)-C(16)121.4(6) N(I)-Cr-N(4) 132.88(14) C(17)-C(16)-C(15)119.7(5) C(2)-N(1)-C(11) 117.3(3) C(12)-C(1?)-C(16)119.3{4) C(2)-N(1)-Cr 121.6(3) C(12)-C(17)-N(2)123.3(4) C(11)-N(1)-Cr 119.2(3) C(16)-C(17)-N(2)117.2(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)119.3(4) C{17)-N(2)-Cr 110.9(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 114.1(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(2l)-N(4)-Cr 123.1(3) C(24)-C(23)-C(28)120.0(5) C(34)-N(4)-Cr 117.0(3) C(25)-C(24)-C(23)120.7(5) N(1)-C(2)-C(3) 123.8(4) C(26)-C(25)-C(24)119.2(5) N(1)-C(2)-C(I) 119.7(4) C(25)-C(26)-C(27)121.7(6) C(3)-C(2)-C(1) 116.5(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)119.1(4) N(2)-C(4)-C(3) 121.9(4) C(23)-C(28)-N(3)118.8(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(11) 121.1(5) C(29)-C(30)-C(31)120.3(4) C(6)-C(7)-C(8) 119.6(5) C(30)-C(31)-C(32)119.5(5) C(9)-C(8)-C(7) 119.7(5) C(33)-C(32)-C(31)119.8(5) C(8)-C(9)-C(10) 120.8(5) C(32)-C(33)-C(34)121.5(4) C(9)-C(10)-C(11)120.2(5) C(33)-C(34)-C(29)117.6(4) C(6)-C(I1)-C(10)118.6(4) C(33)-C(34)-N(4)122.2(4) C(6)-C(I1)-N(1) 120.0(4) C(29)-C(34)-N(4)120.1(4) WO 99/41290 PCT/US99/0186_3 Table 6.3 Structure Determination Summary for((Ph)2nacnac)2Cr C~stal Data Empirical Formula C~4H~4N4Cr Formula Weight 550.65 Crystal color Dark green plates Crystal Size (mm) 0.40 x 0.40 x 0.06 Crystal System triclinic 1o Space Group PI

Unit Cell Dimensions a = 10.54650(10) A

b = 11.4442(2) A

c = 13.8021 (2) A

a =87.5203(9) ~3 = 72.7442(8) y = 65.33 Volume 1439.44(5) ~3 Density (calc.) 1.270 g/cm3 2o Absorption Coefficient 4.27 cm-~

F(000) Data collection Diffractometer Used Siemens P4 Radiation MoKoc (1= 0.710730 Temperature 218(2) K

Monochromator Highly oriented graphite crystal 28 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;"~ = 0.0000%) Observed Reflections 4039 Solution and Refinement System Used SHELXTL (5.03) Solution Direct Methods Refinement Method Full-Matrix Least-Squares Quantity minimized S[w(Fo2 - F~2)2)/S[(wFoz)z~vz 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 = 11.77%, wR = 24.49%

to 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 MW. M~, M~. & M~
The MW, weight average molecular weight, M", number average molecular weight, weighted to the low end of the material, MZ, average weighted to the high end of the material, and MP, 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 (MW) is underestimated proportionately to the additional weight of branches along the backbone. For samples 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 SOOppm 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
1o Chromatography System equipped with 3 Mixed A + 1 SOA Polymer Laboratories (UK) Columns. The measurements are conducted under the following conditions:
Concentration: 2mg/mL
Injection Volume: 400uL
Flowrate: 1 mlJmin Column and Injector Compartment Temperature: 150C
Run Time: 1 Hour The Method of Calculation is: Weight fraction of polymer is weighted against 2o 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", MW, MZ, MP, and D average for the three separate preparations.
Method For Determining Short Chain Branchine (SCB) Samples were analyzed on a Varian Unity+ NMR spectrometer at a magnetic field of 7 Tesla with a lOmm broadband probe tuned for C-13.
Approximately O.Sg of sample was placed in a lOmm NMR tube and filled with 3m1 of a 3:1 1,2,4-trichlorobenzene / deuterated benzene mixture. The 3o 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 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 5 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 Ss 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 l0 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 15 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 Determinintr Melting Point (Peak DSC M.P.) 20 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 25 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°Clmin 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 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 lOM
X0.53MM coating HT SIMDIST CBDF=0.15 UM. At the following conditions: 120°C x Imin x 10°C/min x 150°C x 0 min and RampA:

6.0°C/min x 350°C x Omin.

Polymerization of Ethylene in a NMR Tube Reaction in the Presence Of in-situ (Ph)ZnacnacVMe2[B(C6F5)3l:
Preparation I (in CDaCI~:
0.0453 mmoles ( 15 mg) of (Ph)ZnacnacVMe2, reference Example 3A, and 0.0453 mmoles (23 mg) of B(C6F5)3 were transferred to an NMR tube reactor and CD2Cl2 was vacuum transferred. Ethylene (@ 1 atm.) was charged to the NMR tube and it was closed with a Teflon tap. After 5 minutes, a ~H
NMR spectrum was recorded. Only the ethylene resonance (b 5.40 ppm) and a new peak 8 1.7 ppm was added to the original spectrum, reported in example 3A 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'H 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 C6D6~:

Polymerization of ethylene was also tried in an NMR tube with 4.53x 10-5 moles ( 15 mg) of, reference Example 3A, and 4.53x 105 moles (23 mg) of B(C6F5);. Upon condensing C6D6, (Ph)2nacnacVMe2 and B(C6F5)~
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) ' H NMR (C6D6): broad peaks from 2.4 to 0.6 ppm.

to Polymerization Of Ethylene in a Parr Reactor in the Presence of (Ph)2nacnacVMe2 and Cocatalyst in CH2Cl2:
0.151 mmoles (50 mg) of (Ph)2nacnacVMe2, reference Example 3a, and 0.1 S 1 mmoles of B(C6F5)3 (77 mg) were dissolved in 100 ml of CH2Cl2 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 (D~
water and then dried in a vacuum oven at 60°C overnight. 5.2 grams of polymer were collected. Polymer analysis: MW = 547,700; MW/M~= 2.06; Peak DSC M.P.: 134.2°C.

Polymerization Of Propylene in a NMR Tube Reactor in the Presence of (Ph)ZnacnacVMe2 and Cocatalyst in CDZCl2:
4.53x10-5 moles(15 mg) of (Ph)2nacnacVMe2, reference Example 3a, and 4.53x10-S moles (23mg) of B(C6F5)3 were dissolved in CDZC12 and placed in a NMR tube reactor. Propylene (@ 1 atm.) was then charged to the NMR

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

Polymerization of 1-Hexene in a NMR Tube Reactor in the Presence of (Ph)2nacnacVMeZ 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'H 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.

2o Copolymerization of Ethylene and 1-Hexene in a Parr Reactor in the Presence of (Ph)2nacnacVMe2 and Cocatalyst in CH2Cl2:
0.151 mmoles (50 mg) of (Ph)ZnacnacVMe2, reference Example 3a, and 0.151 mmoles of B(C6F5)3 (77 mg) were dissolved in a solvent mixture of 60 ml of CH2C12 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 (Dn water and then dried in a vacuum oven at 60°C overnight. 5.2 grams of polymer were collected. Polymer analysis: MW = 1,136,000; MW/M" = 2.42; Peak DSC
M.P: 131.4°C;. ~~C NMR: no side chains were indicated.

Polymerization of Ethylene in a NMR Tube Reactor in the Presence of [(Ph)2nacnacVMe(Et20)(THF)][B(C6H~(CF3)z)a] in CDZCl2:
1.88x I 0-5 moles (25 mg) [(Ph)2nacnacVMe(Et20)(TH)~][B(C6H3(CF3)z)a], reference Example 5A, in to 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 ~H NMR spectrum recorded trace amounts of free diethylether peaks along with an intense ethylene monomer peak at 8 5.40 ppm. After allowing the reaction to stand overnight is at room temperature, several particles of polymer were visually observed and ~H 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 I-hexene for ethylene and no polymerization was observed even with heating.

Polymerization of Ethylene in a Parr Reactor in the Presence of [(Ph)2nacnacVMe(Et20)(THF)][B(C6H3(CF3)2)4] in CH2Cl2:
0.045 mmoles (60mg) [(Ph)2nacnacVMe(Et20)(THF)][B(C6H3(CF3)2)al, reference Example 5A, dissolved in 100 ml of CH2C12 was introduced into a Pan reactor. Ethylene (@700 psig) was supplied to the reactor. Once the reactor was pressurized, the 3o 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 WO 99/41290 PCT/US99/018b3 deionized (DI) water and then dried in a vacuum oven at 60°C overnight.
2.5 g of polymer were collected. Polymer analysis: MW = 450,600; M",/M~ = 1.96;
and Peak DSC M.P: 135.9°C.

Polymerization of Ethylene in a Parr Reactor in the Presence of (Ph)ZnacnacVCl2(THF)2 and Cocatalyst in CH2CIZ:
l0 0.776 mmoles (40mg) of (Ph}2nacnacVCl2(THF)2, reference Example 1B, 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.°lo solution in toluene, the color of the solution instantaneously changed to dark red brown. Ethylene (@400 psig) was supplied to the reactor.
15 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 (Dn water and then dried in a vacuum oven at 60°C overnight. 4.6 g of polymer were collected. Polymer analysis:
20 MW = 350,032, M,~/M~ = 10.84.

25 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 1B, was dissolved in 50 ml of toluene in a Parr reactor and 1.2 g 30 (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 by 50 psi. The reaction temperature was maintained under 60°C by cooling water circulation system. The resulting product was washed with a methanol/HCI mixture and deionized (DI) water and then dried in a vacuum oven at 60°C overnight. 4.7 g of white polyethylene polymer was collected.
Polymer Polyethylene analysis: MW = 1,958,584; MW/M~ = 1.75; and Peak DSC M.P : 135.4°C

Polymerization of Ethylene in a Parr Reactor in the Presence of VCI3(TI-IF)3 and Cocatalyst inToluene:
1.20x 10-4 moles (6 mg) of VCI3(THF)~ was dissolved in 50 ml of toluene in a Parr reactor. The color of the solution turned brown and VC 13(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 (DI) water and then dried in a vacuum oven at 60°C overnight. 8.0 g of white polyethylene granules were collected. Polymer analysis: MW = 2,042,158; MW/M" = I.73 and Peak DSC
M.P: I 32.1 °C.

Copolymerization of Ethylene and 1-Hexene in a Parr Reactor in the presence of (Ph)ZnacnacVCl2(THF)2 And Cocatalyst in CH2C12:

7.76 x 10-5 moles (40 mg) of (Ph)2nacnacVCl2(THF)z, reference Example IB, was dissolved in 100 ml of CH2C12 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 I-hexene was added to the reaction mixture.
to 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/HCI mixture and deionized (DI) water and then dried in a vacuum oven at 60°C overnight. 23.6 g of polymer were collected. Polymer analysis:
MW =707,048; MW/M" = 212.33; and total carbons on side chain/1000 carbons by ~ ~C NMR: 48.3.
2o EXAMPLE 17 Polymerization of 1-Hexene in the Presence of (Ph)2nacnacV(Me)Z and Cocatalyst in CHZCl2:
6.04 x 10-5 moles (20 mg) of (Ph)2nacnacV(Me)2, reference Example 3A, was dissolved in 40 ml of dry CHZC12 in an ampoule. MAO (approx. 100 molar eq. in toluene) was added into the solution of (Ph)2nacnacV(Me)2 in the ampoule and the ampoule was closed with a Teflon tap. After two cycles of freeze/pump/thaw, approx. 5 ml of I-hexene was condensed into the ampoule.
3o 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 room temperature. The ampoule was opened to atmosphere and a MeOH/HC1 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: ~H NMR (CDC,~): broad peaks at b 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.
to Polymerization of Ethylene in the Presence of (Ph)2nacnacTiCl2(THF)2 and Cocatalyst in CH2Cl2:
1 s 3.91 x 10-5 moles (20mg) of (Ph)ZnacnacTiCl2(THF)2, reference Example lA, was dissolved in SO ml of CH2C12 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, 2o ethylene (@ I 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: MW = 195,015, M,~,/M" = 21.11; and M.P by DSC=130.6°C
2s EXAMPLE 19 Polymerization of Ethylene in a Parr Reactor in the Presence of (Ph)2nacnacTiCl2(THF)2 and Cocatalyst in CHZCfz:
30 1.57 x 105 moles (8 mg) of (Ph)2nacnacTiCl2(THF)2, reference lA, was dissolved in 50 ml of CH2CI2 and 1.2g (approx. 100 molar eq.) of MAO, 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 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 (DI) water and then dried in a vacuum oven at 60°C overnight. 6. I g of white polyethylene granules were isolated. Polymer analysis: MW = 685,963; MW/M"
= 30.9; and M.P by DSC=132.2°C'.

1o Copolymerization of Ethylene and 1-Hexene in a Parr Reactor in the Presence of (Ph)ZnacnacTiCl2(THF)2 and Cocatalyst in CHZCI2:
3.90 x 10-5 moles (20mg) of (Ph)ZnacnacTiCl2(THF)2, reference Example 1 A, 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 (DI) water and then dried in a vacuum oven at 60°C overnight. 12.5 g of polymer were collected. Polymer analysis: MW = 33,882; M,W/Mn = 218.51; and total carbons on side chain/1000 carbons, by'3C NMR = 34.6.

Polymerization of 1-Hexene in the Presence of (Ph)2nacnacTiCl2(THF)2 and Cocatalyst in CHZC12:
The reaction was performed with 3.90x I 0-5 moles (20 mg) of (Ph)2nacnacTiCl2(THF)2, reference Example lA, MAO (100 eq.) solution and 5 ml of I -hexene in 20 ml of CHIC 1 z in an ampoule sealed with a Teflon 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 5 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.
to EXAMPLE 22 Polymerization of Ethylene in a Parr Reactor in the Presence of (Ph)2nacnacTiCl2(THF)2 and Cocatalyst in Toluene:
15 1.20 x 10-5 moles (8 mg) of (Ph)2nacnacTiCl2(THF)2, reference Example lA, 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 2o 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 (Dn water and then dried in a vacuum oven at 60°C
overnight.
25 10.5 g of white polyethylene granules were collected. Polymer analysis: MW
=
818,850; MW/M" = 28.58; and Peak DSC M.P: 134.2°C.

Polymerization of Ethylene in a Parr Reactor in the Presence of TiCI~(THF)~, and Cocatalyst in Toluene:
1.20 x 10~ moles (6mg) of TiCl3(THF)~ was dissolved in 50 ml of toluene in a Pan reactor. 1.2 g (approx. 100 molar eq.) of MAO, 10 wt.°lo solution in toluene, was added to the TiCI~(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 (DI) water and then dried in a vacuum oven at 60°C
overnight. 3.4 g of white polymer granules were collected. Polymer analysis:
MW = 1,479,060; M",/M" = 153.12; Peak DSC M.P: 134.2°C.

Polymerization of Ethylene in a Parr Reactor in the Presence of (Ph)2nacnacCrCl2(THF)2 and Cocatalyst in CH2Cl2:
7.76 x 10-Smoies (40 mg) (Ph)ZnacnacCrCl2(THF)2, reference Example 1C, and 7.3 g (approx. 100 molar eq.) of MAO, 10 wt.°lo solution in toluene, were dissolved in 100 ml of CH2C 12 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 (DI) water and then dried in a vacuum oven at 60°C overnight. 6.0 g of white polymer powder was collected.
Polymer analysis: MW = 48,613 and MW/M~ = 22.84.

Polymerization of Ethylene in a Parr Reactor in the Presence of (Ph)ZnacnacCrCl2(THF)Z and Cocatalyst in Toluene:
l0 1.20 x 10-5moles (8 mg) (Ph)2nacnacCrCl2(THF)2, reference Example 1 C, arid 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 {D~
water and then dried in a vacuum oven at 60°C overnight. 10.5 g of a white solid polymer was isolated. Polymer analysis: MW: 1,157,039; MW/M": 72.81;
and Peak DSC M.P:134.9°C.

Polymerization of Ethylene in a Parr Reactor in the Presence of CrCl3(THF)~, and 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)~ 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/HC1 mixture and deionized (DI) water and then dried in a vacuum oven at 60°C overnight. 0.5 g of polyethylene were obtained. Polymer analysis: MW = 1,319,817; MW/M" _ 37.88; and Peak DSC M.P: 133.3°C.

Copolymerization of Ethylene and 1-Hexene in a Parr Reactor in the 1o Presence of (Ph)ZnacnacCrCl2(THF)Z 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 CHIC 12 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:
MW = 9,659, MW/M":= 7, M.P. by DSC = 109.6 and 125.4°C and SCB=I6.
2o 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 Pan 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/HCI mixture and deionized (Dn water and then dried in a vacuum oven at 60°C overnight. 250 mg of white rubbery polymer was isolated.
Polymer analysis: MW = 147,054, MW/M":= 82.14, M.P. by DSC = 95.1, I 13.8 and 125.1 °C, and SCB=9.69.

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

Copolymerization of Ethylene and Propylene in a Parr Reactor in the Presence of (Ph)ZnacnacVCl2(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: MW = 1,476,492 MW/M":= 3.94, M.P. by DSC = 117.4°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 (52)

WHAT 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):
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.

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

3. The catalyst system of claim 2 wherein said metal is a group IVB, VB, or VIB transition metal.

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 co-catalyst.

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.

13. The catalyst system of claim 11, wherein said aluminoxane selected from the group consisting of ethyl aluminoxane, isobutyl aluminoxane, and methyl aluminoxane.

14. The catalyst system of claim 11, wherein said alkyl aluminum compound is triethylaluminum.

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

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 IIIB, IVB, VB, VIB, VIIB or VIII 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 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 IVB, 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.

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 R1 and R2 each represent a methyl radical.

25. The compound of claim 15, wherein X represents a BArF-, (phenyl)4B-, (C6F5)4B-, PF6-, BF4-, SbF6- , triflate or p-tosylate group.

26. The compound of claim 15 wherein X represents a BArF-, (C6F5)4B, PF6-, BF4- or SbF6- 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.

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):

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 IIIB, IVB, VB, VIB, 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;

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

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 IIIB, IVB, VB, VIB, 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.

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 IVB, 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.