OLEFIN POLYMERIZATION PROCESS

Abstract: Disclosed herein is a process for the polymerization of ethylene, norbornenes and styrenes, by contacting in solution a selected nickel compound and a selected compound which is or can be coordinated to the nickel with the olefin(s). The polymers produced are useful for films and molding resins.

Description: T TLF OLEFIN POLYMERIZATION PROCESS This application is a continuation-m-part of United States Provisional Application Serial No. 60/000,747, filed June 30, 1995. FTFT.D OF THE INVENTION This invention concerns a process for the preparation of polyolefmε by coordination polymerization of ethylene, styrene or norbornene by a nickel compound coordinated to a selected ligand. TF.ΓTTTJTΓAT, BArra--?nττκm Polyolefms are very important items of commerce, being used for myriad uses, such as molding resins, films, ropes, composites, fibers, elastomers, etc. Suitability for any particular use is dependent on the polymer properties, for instance whether the polymer is elastomeric or thermoplastic. One method of polymerization of these olefms is by coordination polymerization, use of a polymerization catalyst containing a transition metal, the metal usually being thought of as coordinating to one or more species during the polymerization process. Whether any particular transition metal compound is an olefir. polymerization catalyst usually depends on the metal chosen and wha t is coordinated (such as various ligands) to the metal before and during the polymerization. Various transition metal compounds may or may not be active catalysts for a particular (type of) olefin, and the resulting polymer structures may vary. Otner factors such as the efficiency and rate of polymerization may Therefore, new transition metal catalysts for olefm polymerizations are constantly being sought. RtTMMA Y OF THE τrwπnττr> This invention concerns a process for the polymerization of an olefin, comprising: (a) contacting a polymerizable monomer consisting essentially of ethylene, a norbornene or a styrene, and a catalyst system comprising the product of mixing in solution a zerovalent tricoordinate or tetracoordinate nickel compound (II) which has at least one labile ligand, and all ligands are neutral, an acid of the formula HX (IV) , and a first compound selected from the group consisting of: Ar 1 Q n (III) ; R 8 R 10 N-CR 4 5 (CR 6 R 7 ) m -NR 8 R 10 (V) Ar " - (XVII) ; H,N H 2 N, ,P(OH) 2 "C0 2 H (XVIII) ; (XIX) OR" (XXVI) ; ArKTN S NHAr 1c <χχvil) ; R 22 R 23 R 24 P (XXVIII) ; (XXXVI) ; and R £ S- CR R 5 (CR 6 R 7 ) m -SR £ (XXXVII ) ; wherein • X is a noncoordmatmg anion ; A A „ rr 1 lis an aromatic moiety with n free valencies, diphenylmethyl; each Q is -NR 2 R J or -CE 9 -ffi 3 ; n is 1 or 2; E is 2-thιenyl or 2-furyl; 2 each R is independently hydrogen, benzyl, substituted benzyl, phenyl or substituted phenyl; g each R is independently hydrogen or hydrocarbyl; and each R is independently a monovalent aromatic moiety; F 4 ~ is hydrogen or alkyl; each R , R , R , and R is independently hydrogen, hydrocarbyl or substituted hydrocarbyl; each R is independently hydrocarbyl or substituted hydrocarbyl containing 2 or more carbon atoms; each R is independently hydrogen, hydrocarbyl or substituted hydrocarbyl; r' is an aryl moiety; R", *3 , and R are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group; F 11 and R 1 are each independently hydrocarbyl, substituted hydrocarbyl or an inert functional group whose E s is about -0.4 or less; each R and R is independently hydrogen or acyl containing 1 to 20 carbon atoms; Ar is an aryl moiety; R 1B and R 19 are each independently hydrogen or hydrocarbyl; Ar 4 is an aryl moiety; Ar 5 and Ar are each independently hydrocarby; Ar 7 and Ar8 are each independently an aryl moiety; Ar 9 and Ar 1 are each independently an aryl moiety or -C0R 25 , wherein R 25 is alkyl containing 1 to 20 carbon atoms; Ar 11 is an aryl moiety; R 41 is hydrogen or hydrocarbyl; Ls hydrocarbyl or -C (O) -NR 41 -Ar l:ι R 44 is aryl ; R 2i and R 23 are each independently phenyl groups substituted by one or more alkoxy groups, each alkoxy group containing l to 20 carbon atoms; and R 24 is alkyl containing 1 to 20 carbon atoms, or an aryl moiety. This invention also concerns a catalyst for the polymerization of ethylene, a norbornene, or a styrene, comprising, the product of mixing in solution a zerovalent tricoordinate or tetracoordmate nickel compound (II) which has at least one labile ligand and all ligands are neutral, an acid of tne formula HX (IVj , and a compound selected from the group consisting of. Ar^-Qn (III) ; R 8 R 10 N-CR 4 R 5 (CR 6 R 7 ) m -NR 8 R 10 (V) ; (XX) ; (XXI) ; (XXIII 1 Ar 9 HK s NHAr ι (XXVI ) ; ( XXVII ) R 22 R 23 R 24 p ( χχvI I I ) . (XXXVI) and R ε S-CR 4 R 5 (CR 6 R 7 ) m -SR ε (XXXVII); wherein. X is a noncoordmatmg anion; Ar is an aromatic moiety with n free valencies, or diphenylmethyl; each Q is -NR 2 R 43 or -CR 9 =NR 3 ; E is 2-thιenyl or 2-furyl; R 4 is hydrogen or alkyl; 2 each R is independently hydrogen, benzyl, substituted benzyl, phenyl or substituted phenyl; each R is independently a monovalent aromatic moiety; g each R is independently hydrogen or hydrocarbyl; m is 1, 2 or 3; each R , R , R , and R is independently hydrogen, hydrocarbyl or substituted hydrocarbyl; g each R is independently hydrocarbyl or substituted hydrocarbyl containing 2 or more carbon atoms; each R is independently hydrogen, hydrocarbyl or substituted hydrocarbyl; Ar' is an aryl moiety; " ", R 1" , and R are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group; R 11 and R 1" are each independently hydrocarbyl, substituted hydrocarbyl or an inert functional group whose E s is about -0.4 or less; each R ιε and R 1 is independently hydrogen or acyl containing 1 to 20 carbon atoms; Ar J is an aryl moiety; R ιε and R 19 are each independently hydrogen or hydrocarbyl; Ar 4 is an aryl moiety; Ar 5 and Ar are each independently hydrocarby; - 8 Ar and Ar are each independently an aryl moiety; Ar' and Ar are each independently an aryl moiety, - CO^ *", or Ar' and Ar taken together are a divalent aromatic moiety and wherein R 25 is alkyl containing I to 20 carbon atoms; Ar" is an aryl moiety; R 41 is hydrogen or hydrocarbyl; R 4 ~ is hydrocarbyl or -C(0) -NR 41 -Ar l:L ; R 2 ' and p 3 are each independently phenyl groups substituted by one or more alkoxy groups, each alkoxy group containing 1 to 20 carbon atoms; and R 24 is alkyl containing 1 to 20 carbon atoms, or an aryl moiety; and provided that the molar ratio of (III), (V) (XVI), (XVII), (XVIII), (XIX), (XX), (XXI), (XXII), (XXIII), (XXIV), (XXV) , (XXVI) , (XXVII) , (XXVIII) , (XXXVI) or (XXXVII) : (II) is about 0.5 to about 5, and the molar ratio of (IV) : (II) is about 0.5 to about 10. This invention also concerns a process for the polymerization of an olefin, comprising, contacting ethylene, a norbornene, or a styrene with a nickel [II] complex of a ligand selected from the group consisting of : Ar^-Qn (III); R 8 R 10 N-CR 4 R 5 (CR 6 R 7 ) m -NR 8 R 10 (V) ; H,N S ,P(OH) 2 * C0 2 H (XVIII) (XIX) ; OR" NHAr 10 (XXVI I ) ; R 22 F I : R 24 P (XXVIII ) ; (XXXVI ) , and R ε S - CR 4 R 5 (CR 6 R 7 ) m - SR 8 (XXXVI I ) ; wherein - X is a noncoordmatmg anion; Ar is an aromatic moiety with n free valencies, or diphenylmethyl ,- each Q is -NR 2 R 43 or -CR 9 =NR 3 ; R 4 ~ is hydrogen or alkyl; n is 1 or 2, E is 2-thιenyl or 2-turyl, 2 each R is independently hydrogen, benzyl, substituted benzyl , pnenyl or substituted phenyl, 3 each R is independently a monovalent aromatic moiety, c each R is independently hydrogen or hydrocarbyl; is i, each R , R , R , and R is independently hydrogen, hydrocarbyl or substituted hydrocarbyl; each R is independently hydrocarbyl or substituted hydrocarb-_,1 containing 2 or more carbon atoms; each R is independently hydrogen, hydrocarbyl or subs i uted hydrocarbyl, Ar' is an aryl moiety, F 1 ", " , and R 14 are each independently hydrogen, πydrocarby , substituted hydrocarbyl or an inert functional group, F 1 ' and R 1" are each independently hydrocarbyl, substituted hydrocarbyl or an inert functional group whose E s is about -0 4 or less; each R 16 and R 1 is independently hydrogen or acyl containing 1 to 20 carbon atoms; Ar J is an aryl moiety,- R R 11!8 and R 19 are each independently hydrogen or hydrocarbyl; Ar 4 is an aryl moiety; Ar 5 and Ar are each independently hydrocarby; 7 8 Ar and Ar are each independently an aryl moiety,- Ar ' and Ar are each independently an aryl moiety, - C0 2 R 25 , or Ar and Ar 6 taken together are a divalent aromatic moiety and wherein R is alkyl containing 1 to 20 carbon atoms,- Ar x is an aryl moiety; R 4 ' is hydrogen or hydrocarbyl; R 42 is hydrocarbyl or -C(O) -NR 41 -Ar 1:L ; R 44 is aryl; 22 23 R and R are each independently phenyl groups substituted by one or more alkoxy groups, each alkoxy group containing 1 to 20 carbon atoms; and P. 2 ' is alkyl containing 1 to 20 carbon atoms, or an aryl moiety. Described herein is a process for the polymerization of olefms, comprising, contacting ethylene, a norbornene or a styrene with a nickel containing first compound of the formula [L 1 ς : r L 2 s L 4 t Nι] " x " (XXXIII) , wherein: i is a first monodentate neutral ligand coordinated to said nickel, i is a second monodentate neutral ligand coordinated to said nickel which may be said first monodentate neutral ligand and r is 0 or 1, or and taken together are a first bidentate neutral ligand coordinated to said nickel and r is 1; L " and taken together are a π-allyl ligand coordinated (XXXII) coordinated to said nickel, or L is a third neutral monodentate ligand selected from the group consisting of ethylene, a norbornene and a styrene or a neutral monodentate ligand which can 4 3ε be displaced by an olefin, and L is R ; X is a relatively non-coordinating anion,- each of g, s and t is 1; said first monodentate neutral ligand and said first bidentate neutral ligand are selected from the group consisting of Ar 1 Q n (III) ; R 8 R 10 N-CR 4 R 5 (CR 6 R ) m -NR 8 R 10 (V) ; Ar " -NHR 1 ' (XVI) ; (XVII) (XXIII) ; NHAr 10 (χχvil) R 22 R 23 R 24 p (χχvIII) . (XXXVI) ; and R 8 S-CR 4 R 5 (CR 6 R 7 ) m -SR 8 (XXXVII) ; Ar is an aromatic moiety with n free valencies, or diphenylmethyl; each Q is -NR 2 R 43 or -CR 9 =NR 3 ; R ' is hydrogen or alkyl,- n is 1 or 2; E is 2-thienyl or 2-furyl; 2 each R is independently hydrogen, benzyl, substituted benzyl, phenyl or substituted phenyl; q each R is independently hydrogen or hydrocarbyl; and each R is independently a monovalent aromatic moiety; m is 1, 2 or 3; each R , R , R , and R is independently hydrogen, hydrocarbyl or substituted hydrocarbyl; p each R is independently hydrocarbyl or substituted hydrocarbyl containing 2 or more carbon atoms,- each R is independently hydrogen, hydrocarbyl or substituted hydrocarbyl; Ar' is an aryl moiety; P." 1 ", P. 1" , and R are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group; F ' and R 15 are each independently hydrocarbyl, substituted hydrocarbyl or an inert functional group whose E s is about -0.4 or less; each K xt and R ' is independently hydrogen or acyl containing 1 to 20 carbon atoms,- Ar 3 is an aryl moiety; R ιε and R 19 are each independently hydrogen or hydrocarbyl; Ar "* is an aryl moiety,- Ar 5 and Ar 6 are each independently hydrocarby; Ar' and Ar are each independently an aryl moiety; Ar 9 and Ar 1 are each independently an aryl moiety or -C0R 25 , wherein R 25 is alkyl containing l to 20 carbon atoms,- Ar is an aryl moiety; R 4-L is hydrogen or hydrocarbyl; R 42 is hydrocarbyl or -C(O) -NR 41 -Ar 11 ; R 22 and R 23 are each independently phenyl groups substituted by one or more alkoxy groups, each alkoxy group containing 1 to 20 carbon atoms; and R is alkyl containing 1 to 20 carbon atoms, or an aryl moiety; R is hydrocarbylene; F 3e is hydrogen, alkyl, or -C(0)R 39 ; each P. 37 is hydrocarbyl or both of R 37 taken together are hydrocarbylene to form a carbocyclic ring; R 3B is hydride, alkyl or -C(0)R 39 ,- and R" is hydrocarbyl R 44 is aryl. Also described herein is a compound of the formula [L 1 ς L 2 r 3 ε 4 t Ni] + X " (XXXIII), wherein: i is a first monodentate neutral ligand coordinated to said nickel, 1 is a second monodentate neutral ligand coordinated to said nickel which may be said first monodentate neutral ligand and r is 0 or 1, or 1 and L 2 taken together are a first bidentate neutral ligand coordinated to said nickel and r is 1; L J and L 4 taken together are a π-allyl ligand coordinated to said nickel, L and L taken together are (XXXII ) coordinated to said nickel, or L is a third neutral monodentate ligand selected from the group consisting of ethylene, a norbornene and a styrene or a neutral monodentate ligand which can De displaced by an olefin, and L 4 is R 38 ; X is a relatively non-coordinating anion; q, s and t are each 1; said first monodentate neutral ligand and said first bidentate neutral ligand are selected from the group consisting of Ar 1 Q n (III); R 8 R 10 N-CR 4 R 5 (CR 6 R 7 ) m -NR 8 R 10 (V) ; (XIX) ; (XXIII ; (XXVI) ; Ar 9 HK S NHAr 10 (χχvil) ; R 22 R 23 R 2 P (XXVIII) ; (XXXVI) and R 8 S-CR 4 R 5 (CR 6 R 7 ) m -SR 8 (XXXVII) ; wherein: Ar is an aromatic moiety with n free valencies, or diphenylmethyl, each Q is -NR 2 R 43 or -CR 9 =NR 3 , R 4~ is hydrogen or alkyl; n is 1 or 2, E is 2-thιenyl or 2-furyl; 2 each R is independently hydrogen, benzyl, substituted benzyl, phenyl or substituted phenyl; 9 each R is independently hydrogen or hydrocarbyl; and each R is independently a monovalent aromatic moiety, m is 1, 2 or 3, each R , R , R , and R is independently hydrogen, hydrocaroyl or substituted hydrocarbyl, p each R is independently hydrocarbyl or substituted hyαrocarbyl containing 2 or more carbon atoms, each R is independently hydrogen, hydrocarbyl or suostituteα hydrocarbyl, Ar^ is an aryl moiety, R 12 , R 13 , and R 4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group, F" and R 1:5 are each independently hydrocarbyl, substituted hydrocarbyl or an inert functional group whose E £ is about -0 4 or less, each R ιe and R is independently hydrogen or acyl containing 1 to 20 carbon atoms, Ar 3 is an aryl moiety, F lε and R 9 are each independently hydrogen or hyαrocaroyl, Ar 4 is an aryl moiety; Ar and Ar are each independently hydrocarby; Ar " and Ar 8 are each independently an aryl moiety; Ar 9 and Ar 1 are each independently an aryl moiety or -CO : F'", wherein R 25 is alkyl containing 1 to 20 carbon atoms, Ar 3"1 is an aryl moiety, R 41 is hydrogen or hydrocarbyl; R 42 is hydrocarbyl or -C(O) -NR 41 -Ar 11 ; F" and R " are each independently phenyl groups substituted by one or more alkoxy groups, each alkoxy group containing 1 to 20 carbon atoms; and R^ is alkyl containing 1 to 20 carbon atoms, or an aryl moiety; R" = is hydrocarbylene; R 3e is hydrogen, alkyl, or -C(0)R 39 ; each R 3 ' is hydrocarbyl or both of R 37 taken together are hydrocarbylene to form a carbocyclic ring; R 38 is hydride, alkyl or -C(θ)R 3S ; and R 39 is hydrocarbyl. Described herein is a compound of the formula (XXIV) wnerein E is 2-thιenyl or 2-furyl; Ar" and Ar are each independently hydrocarby. DETAILS OF HE TNVENTTΩN Tne olefins polymerized herein are ethylene, a styrene and a norbornene . Norbornene and styrene may be present m the same polymerization, and a copolymer may be produced By a styrene herein is meant a compound of the formula (XXIX) wherein R 2c , R 27 , R 26 , R 29 and R are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, all of which are inert in the polymerization process. It is preferred that all of R 26 , R 26 , R 29 and R 30 are hydrogen. By "a norbornene" is meant that the monomer is characterized by containing at least one norbornene-functional group in its structure including norbornadiene as identified by the formulas below, which can be substituted or unsubstituted (XXXIV) wherein ,x a" represents a single or double bond. Representative monomers are compounds (XXXV) and (XXXX) as follows: (XXXIV) ; (XXXX) wherein R 4 , R 4 , R , and R independently are hydrogen halogen, or hydrocarbyl, provided that, except if the hydrocarbyl group is vinyl, if any of the hydrocarbyl are alkenyl, there is no terminal double bond, i.e., the double bond is internal; or R 46 and R 48 taken together can be part of carbocyclic ring (saturated, unsaturated or aromatic) ; or R and R and/or R and R ' taken together are an alkylidene group. In these structures "z" is 1 to 5. Examples of such norbomenes include norbornadiene, 2- norbornene, 5-methyl-2-norbornene, 5-hexyl-2-norbornene, 5- ethylidene-2-norbornene, vinylnorbornene, dicyclopentadiene, dihydrodicyclopentadiene, tetracyclododecene, trimers of cyclopentadiene, halogenated norbomenes wherein R 4 , R 47 , R 48 and R 49 may also be halogen or fully halogenated alkyl groups such as C F 2 -ι wherein w is 1 to 20, such as perfluoromethyl and perfluorodecyl. The halogenated norbo enes can be synthesized via the Diels-Alder reaction of cyclopentadiene an appropriate dieneophile , such as F 3 CC≡CCF 3 or R 49 2 C=CR 49 C w F 2w+1 wherein each R 49 is independently hydrogen or fluorine and w is 1 to 20. It is also preferred that in the polymerization processes described herein that the polymer produced has an average degree of polymerization of about 10 or more, more preferably about 20 or more, and especially preferably about 50 or more. In the polymerization processes and catalyst compositions described herein certain groups may be present. By hydrocarbyl is meant a univalent radical containing only carbon and hydrogen. By saturated hydrocarbyl is meant a univalent radical which contains only carbon and hydrogen, and contains no carbon-carbon double bonds, triple bonds and aromatic groups By substituted hydrocarbyl herein is meant a hydrocarbyl group which contains one or more (types of) substitutents that does not interfere with the operation of the polymerization catalyst system Suitable subεtituents include halo, ester, keto (oxo) , ammo, immo, carboxyl, phosphite, phosphonite, phosphme, phosphmite, thioether, amide, nitrile, and ether Preferred substituentε are halo, ester, ammo, immo, carboxyl, phosphite, phosphonite, phosphme, phosphmite, thioether, and amide By benzyl is meant the C6H5CK2- radical, and substituted benzyl is a radical m which one or more of the hydrogen atoms is replaced by a substituent group (which may include hydrocarbyl) . By phenyl is meant the C-5K5- radical, and a phenyl moiety or substituted phenyl is a radical in which one or more of the hydrogen atoms is replaced by a substituent group (which may include hydrocarbyl) Preferred substituents for substituted benzyl and phenyl include those listed above for substituted hydrocarbyl, plus hydrocarbyl. If not otherwise stated, hydrocarbyl, substituted hydrocarbyl and all other groups containing carbon atoms, such as alkyl, preferably contain 1 to 20 carbon atoms. By an aromatic moiety herein is meant a radical containing at least one carbocyclic or heterocyclic aromatic ring, which has a number of free valences to the carbon atoms of the aromatic carbocyclic rmg(s) . A monovalent aromatic moiety has one free valence, and herein is termed an aryl moiety. If there is more than one aromatic ring the radical, the ring may be joined by covalent bonds (as m biphenyl) or may be fused (as m naphthalene) , or both. The free valencies may be at carbon atoms in one ring, or more than one ring if more than one ring is present. The aromatic rmg(ε) may be substituted by hydrocarbyl groups or other substitutentε which don't interfere with the catalytic activity of the catalyst system. Substituents that aid the polymerization may be present. Suitable and preferred substituents are as liεted above for substituted hydrocarbyl groups. Suitable aromatic radicals herein include phenyl, o- phenylene, 1, 8-naphthylene, and 2-thiophenyl. A transition metal compound which may be initially added to a polymerization process mixture is (II) , a zerovalent nickel compound which is tricoordinate or tetracoordinate. Also included within the definition of this zerovalent nickel compound are mixtures of compounds which will generate suitable zerovalent nickel compounds m situ, such as mixtures of nickel compoundε m higher valence states with suitable reducing agents. The ligands which are coordinated to the nickel atom may be monodentate or polydentate, so long as the nickel compound is tricoordinate or tetracoordinate. The ligandε should be such that at least two, and preferably all, of the coordination sites of the nickel atom are coordinated to ligands which are readily, reverεibly or irreverεibly, diεplaceable by (III) , (V) , or any one of (XVI) to (XIXi , (XXXVI) and (XXXVII) . Such readily displaceable ligands include η 4 -l, 5-cyclooctadiene and tris (o-tolyl)phosphite (which is a phosphite with a large cone angle) , ethylene and carbon monoxide. A preferred nickel compound (II) is bis(η 4 -1,5- cyclooctadiene)nickel [0] . By the compound HX lε meant the acid of a noncoordmatmg monoanion, or the equivalent thereof, i.e., a combination of compounds that will generate this acid. Noncoordmat g anions are well known to the artisan, see for instance . Beck., et al. , Chem. Rev., vol. 86, p. 1405-1421 (1988), and S. H. Strauss, Chem. Rev., vol. 93, p. 927-942 (1993), both of which are hereby included by reference. Relative coordinating abilities of such noncoordmatmg anions are described in these references, Beck at p. 1411, and Strauss at p. 932, Table III. Also useful in this process m place of HX are "solid" acids, such as acidic aluminas, clays and zirconias, which are considered herein to be acids with relatively non-coordinating anions. Preferred anions X are BF " , PF 6 " , and BAF {tetrakis [3, 5- biε (trifiuoromethyl)phenyl]borate} , SbF~ , and BAF is especially preferred. The acids of these anions are known, for instance HBF 4 is commercially available, and HBAF can be made by the method described m K. Brookhart, et al., Organometallics, vol. 11, p. 3920-3922 (1992) . In all forms of (III) it is preferred that R and R 43 are hydrogen. If R 43 is alkyl, it is preferred that it is methyl. In 2 all forms of (III^ , each R may be independently hydrogen, hydrocarbyl or substituted hydrocarbyl, and it is preferred that 2 eeaacchh RR 2 iiss hhyyddrrooggee:n, benzyl, substituted benzyl, phenyl or substituted phenyl In one preferred form of (III), n is 1 and Q is -NR 2 R 43 . It 2 1 s preferred that P. is hydrogen and that Ar is 2, 6-dialkylphenyl or a iαe, carboxy, or keto substituted phenyl. More preferably, Ar is 2, 6-dιιsopropylphenyl, 2-carbomoylphenyl, 2-carboxyphenyl, or 2-benzoylphenyl . In another preferred form of (III) , n is 2 and each Q is -NR -'R'""- . In this instance it is more preferred that R2 is hydrogen, and/or Ar is o-phenylene or 1, 8-naphthylene, and it is especially preferred that Ar is 1, 8-naphthylene. 9 3 In (III) , when n is 1 and Q is -CR =NR , it is preferred c 3 that R" is hydrogen, and R is preferably 2,6-dialkylphenyl, or amide, ester, carboxyl, keto, or halo substituted phenyl. More preferably, R J is 2,6-dιιsopropylphenyl, 2-carbomoylphenyl, 2- carbomethoxyphenyl, 2-carboxyphenyl, l-fluoren-9-onyl, 1- anthraσumolyl, or pentafluorophenyl. Ar is aryl, or halo, ester, ammo, imino, carboxyl, phosphite, phosphonite, phosphine, phosphmite, ether, thioether, or amide substituted phenyl. More preferably, Ar 1 is diphenylmethyl, 9-anthracenyl, 2-furanyl, 2- thiofuranyl, 2-phenolyl, or 2-hydroxy-naphthyl. When Ar 1 is diphenylmethyl, these tautomeric forms are believed to exist when these compounds are complexed to nickel. 9 3 When in (III) n is 2 and Q is -CR =NR , it is preferred that Ar 1 is p-phenylene, and that R is 2,6-disubstituted phenyl in which the substitutents are halo, alkyl, or halo and alkyl. In (III) , when Q is -NHR 2 , R 2 taken together with Ar 1 may form a carbocyclic or heterocyclic ring, as long as the atom of R attached directly to the nitrogen atom is a saturated carbon atom. Thus another preferred compound (III) is It will be noted that there are actually two amino groups in this compound that meet the criteria for Q. This is compound 105, below. For (V) it is preferred that m is 1, all of R 4 , R 5 , R 6 , R 7 and R 10 are hydrogen, and both of R are 2,6-dιalkylphenyl, eεpecially ,6-dιιsopropylphenyl, or cyclohexyl In another preferred compound (V) m is 1, all of R , R , R , and R are hydrogen, both of R 8 are phenyl, and both of R10 are ethyl . In (V) too much or too little steric hindrance around the nitrogen atoms may cause a catalytic composition containing such a compound to be ineffective as an olef polymerization catalyst. In (XVI) is preferred that Ar is phenyl, 2-pyridyl, or 3- hydroxyl-2-pyrιdyl, and/or R is hydrogen, phenyl, 2,6- dnεopropylphenyl, l-naphthyl, -methyl-1-naphthyl, or 2- phenylpnenyl Ir. (XVII) it is preferred that R Δ and R 14 are hydrogen, and/or F~" is hydrogen or t-butyl, and/or R and R are both t- butyl or both phenyl, and/or R is t-butyl and R " is 2-hydroxy- 3 , 5-dι-t-butylphenyl . Note that when R 15 lε 2-hydroxy-3, 5-dι-t- butylpnenyl the compound contains 2 phenolic hydroxy groups, both of which are steπcally hindered. The steric effect of various groupings has been quantified by a parameter called E s , see R. W. Taft, Jr., J. Am. Chem. Soc, vol. 74, p. 3120-3128 (1952), and M.S. Newman, Steric Effects m Organic Chemistry, John Wiley & Sons, New York, 1956, p. 598-603. For the purposes herein, the E s values are those described m these publications. If the value for E s for any particular group is not known, it can be determined by methods described in these publications. For the purposes herein, the value of hydrogen is defined to be the same as for methyl. It is preferred that the total E £ value for the ortho (or other substituents closely adjacent to the -OH group) substitutents m the ring be about -1.5 or less, more preferably about -3.0 or less. Thus a compound εuch as 2,4, 6-trι-t-butylphenol only the E s valueε for the 2 and 6 substituted t-butyl groups would be applicable I Inn ((XXXX)) iitt iiss pprreeffeerrrreedd tthhaatt bbootthh RR 16 aanndc R are hydrogen or that both are acyl. A preferred acyl group is CH 3 C(O) - . In (XXI) it is preferred that Ar 3 is phenyl or substituted phenyl, more preferably phenyl. In (XXII) it is preferred that both of R iD and R are methyl, or both are hydrogen. In (XXIII) it is preferred that Ar is phenyl or substituted phenyl, more preferably phenyl. In (XXIV) it lε preferred that Ar and Ar are independently phenyl substituted phenyl, or cyclohexyl, and it is especially preferred when both are cyclohexyl or both are phenyl. In (XXVI) it is preferred that Ar and Ar are independently phenyl or subεtituted phenyl. In a specific preferred compound, Ar - is phenyl or p-tolyl and Ar8 lε 2,6-dιιsopropylphenyl. In (XXVII) it is preferred that R 25 lε methyl. Specific preferred compounds are Note that in one of these compounds there are 2 thiourea groups present. In (XXVIII) it is preferred that R R 23 and R 24 are each independently o-tolyl, 2, ,6-trιmethoxyphenyl, 2,6 di ethoxyphenyl, -methoxyphenyl, and 2,3,6-trimethoxyphenyl. Other preferred groups for R ,24 are ethyl, isopropyl and phenyl. It is also preferred that R ,24 is an aryl moiety. In another preferred form, when R 22 , R 23 and/or R 4 are phenyl or substituted phenyl, there is at least one alkoxy group, preferably a methoxy group, ortho (in the benzene ring) to the phosphorous atom. Another compound (XXVIII) is 1,3-bιs [ (bιs-2,6- dimethoxyphenyDphosphino]propane. This compound actually has two phosphine groups that each structurally meet the requirements for a compound of type (XXVIII ) . It is also preferred that each of R 22 , R 23 , and R 24 (when it is an aryl moiety) contain electron donating groups bound to the aromatic moiety through a carbon atom of an aromatic ring. The concept of electron donating groups is well known to the artisan. One method of measuring the electron donating ability of a group (particularly in a benzene ring, but it is not limited to such rings) which is not adjacent to the "active" center is by using the Hammett equation, see for instance H. H. Jaffe, Chem. Rev., vol. 53, p. 191-261 (1953). The actual result of this is called the Hammett σ constant. For ortho (adjacent) substituents one may use the Taft σ* constant as determined by measurements on ortho- benzoate esters, see for instance R. w. Taft, Jr., J. Am. Chem. Soc, vol. 74, p. 3120-3128 (1952); ibid., vol. 75, p. 4231-4238 (1953) ,- and C. K. Ingold, Structure and Mechanism in Organic cne istry, 2nd Ed., Cornell University Press, Ithaca, 1969, p. 1220-1226. It is preferred that the total of the σ and σ* constants for any of the groups R 22 , R 23 , and R 24 (when it is an aryl moiety) be about -0.25 or less, more preferably about -0.50 or less (it is noted that the σ and σ* constants for electron donating groups are negative, so the more electron donating groups present, the more negative this total becomes) and especially preferably about -0.75 or less. In (XXXVI) it is preferred that Ar 11 is 2,6-dιalkylphenyl, more preferably 2,6-dimethylphenyl or 2,6-dιιsopropylphenyl It is preferred that R 42 is -C(O) -NR 41 -Ar 11 . It is preferred that R 41 is hydroge . In (XXXVII) it is preferred that m is l, and/or all of R 4 , R s , R € and R 7 are hydrogen, and/or both of R 8 are aryl moieties, more preferably both of R are 2,6-dιalkylphenyl, and especially preferably both of R are 2,6-dimethylphenyl. In some of the compounds herein, the group -CHPh 2 , diphenylmethyl, may appear, especially when the methme carbon atom can be bound to the carbon atom of an imine. In this case one can write such a compound as -N=CH-CHPh 2 (the imme form) or as -NH-CH=CPh 2 (amme form) . It has been found that in the free compounds (not complexed to nickel) this group is usually m the am e form However, in a few of the nickel complexes of these types of compounds the preliminary evidence indicates the ligand is preεent the imme form Therefore, one may consider these forms interchangeable for the purposes herein, and it is noted that both types of compounds are mentioned in the claims herein. The ligands can be made by methods that can be readily found 10 the literature, and/or are available commercially or form lanoratory supply houses, or are described in the Examples herein The polymerization may also be carried out by [ 1 σ L 2 r L 3 ε L 4 t Nι] + X " (XXXIII), which may be formed in situ or added directlv to the initial polymerization mixture For example, 15 (XXXIII) may be the form of a π-allyl complex By a π-allyl gro p is meant a monoaniomc radical with 3 adjacent εp carbon atoms bound to a metal center in an η fashion The three sp" caroon atoms may ne substituted with other hydrocarbyl groups or functional groups Typical π-allyl groups include 0 CO,R wherein R is hydrocarbyl. In (XXXIII) when it is a π-allyl type complex, L" and L -* taken together are the π-allyl group. As shown "> many of the Examples herein, these π-allyl compounds may be stable, and may be used themselves to initiate the olef polymerization Initiation with π-allyl compounds may be sluggish at times Initiation of π-allyl compounds can be improved by using one or 30 more of the following methods- • Using a higher temperature such as about 80°C • Decreasing the bulk of the ligand, such as R 2 and R 5 being 2,6-dimethylphenyl instead of 2,6-dιιsopropylphenyl. • Making the π-allyl ligand more bulky, such as using 35 rather than the simple π-allyl group itself. • Having a Lewis acid present while using a functional π-allyl Relatively weak Lewis acids such a triphenylborane, tris (pentafluorophenyl)borane, and tris (3,5- trifluoromethylphenyDborane, are preferred Suitable functional groups include chloro and ester. "Solid" acids such as mont orillonite may also be used. However, (XXXIII) may also be present in the polymerization in other "forms" For instance, L may be an olefin, such as ethylene, a norbornene or a styrene or a ligand capable of being displaced by an olefm. By a ligand capable of being displaced by an olefin is meant that the ligand is more weakly coordinating to nickel than an olefin, and when in the complex is in contact with an olefin, the olefin displaces it. Such ligands are known in the art and include dialkyl ethers, tetrahydrofuran and mtriles such as acetonitrile. When J is an olefin, L 4 may be -R 35 R . R 35 is alkylene, but it actually is a "polymeric" fragment with one or more repeat units (derived from the olefin(s) being polymerized) making up R 35 In th s form (XXXIII) may be said to be a living ended polymer, further polymerization adding more repeat units to R R 3ε may oe thought of as the end group of the polymeric group R ", and may be derived from the similar grouping such as R 38 which was originally coordinated to the nickel. Wnen L 3 and L 4 in (XXXIII) taken together are (XXXII), (XXXIII) may also be thought of aε a living polymer Thiε type of grouping lε often referred to as an "agostic" coordination, and in this group -R R may be thought of in the same way as described above Whether a living ended molecule will be in a form with a coordinated olefm or contain (XXXII) will depend on the other ligands coordinated to nickel, and the nature of the olefm being polymerized It is believed that cyclic olefins tend to have living ends containing agostic groupings. In (XXXIII) it is preferred that r is 1. The second monodentate neutral ligand may be any ligand which fits this description, including being the same as the first neutral monodentate ligand. Oftentimes though this ligand is a dialkyl ether such as diethyl ether or an aliphatic nitrile such as acetonitrile, or tetrahydrofuran By "neutral" in the context of (XXXIII) is meant that the ligand is electrically neutral, i.e., is not charged In (XXXIII) preferred structures for the first ^ neutral monodentate ligand are those shown above However, in certain circumstances, L 1 and L2 may be a single neutral bidentate ligand of the same formula as when L is a neutral monodentate ligand In other words, some of the compounds (III), (V), (XVI) to (XXVIII; , (XXXVI) and (XXXVII) may act as bidentate ligands m 0 (XXXIII) This may depend on the ligand itself, what the ratio of liganc to Ni is, what the other ligands may be, and whether there are any other compounds present which may also act as ligands Wner r in (XXXIII) is zero, simple dimers (containing 2 Ni atomε) with bridging ligands of the compound [L 1 L 3 L 4 Nι] + x " are ^ also included within the definition of (XXXIII) For instance a dimer containing L , r is zero, and L and L are combined into an π-allvi group could have the formula In this structure both L 1 ligands are bridging between the 2 0 nickel atomε Tniε type of dimer lε familiar to thoεe skilled m tne ait, and is believed to readily disassociate into "monomeric" nickel compounαε on exposure to olefin. Some of the formε of (XXXIII) are relatively unεtable, and are difficult to isolate as pure compounds Nevertheless their 5 presence can be demonstrated by various methodε known in the art For instance, "living end" and other forms of (XXXIII) may be detected in solution by nuclear magnetic resonance (NMR) analysis, especially a combination of H and C NMR. Such detection of living ends is usually best done when R contains relatively few 0 repeat units (XXXIII) may be made by methods described herein, especially in the Examples, or may actually be formed m situ at the beginning of or during the polymerization process. It is believed that when (III) , (V) , (XVI) to (XXVIII) , (XXXVI) or (XXXVII) , and (II) and HX are mixed together in solution a coordination compound such as (XXXIII) is formed which is active as a catalyst for the polymerization of olefinε Tne preparation of one of the catalyst systems, when (II) is used, may be carried out m solution By solution is meant that (II) and (III), (V), (XVI) to (XIX), (XXXVI) or (XXXVII), and (IV) are at least initially somewhat soluble m the solvent chosen. By somewhat soluble lε meant that at least a 0.01 molar solution of each of the components in the solvent may be formed under process conditions This catalyst system may them be removed from the solvent, as by evaporation of the solvent under vacuum, and then contacted with one or more olefms to carry out the polymerization However, it is preferred to carry out the polymerization in the presence of the "original" solvent in which the active catalyst is formed One or more of the components, including tne polymer produc , may become insoluble aε the polymerization proceedε Uεeful solvents include hydrocarbons such as toluene or benzene. Benzene is a preferred solvent. The benzene used herein is benzene-dβ. Although it is not critical, when (II) lε present it is preferred that the molar ratio of (III) , (V), (XVI) to (XXVIII), (XXXVI) or (XXXVII) : (II) lε about 0.5 to 5, and the molar ratio of (I i (II) lε about 0.5 to about 10. It lε alεo preferred that all the polymerizations be carried out at a temperature of about -100°C to about +200°C, more preferably about -20°C to about +100°C Tne polymers produced by this procesε are useful as molding resins, films and elaεtomerε Moεt of the formulaε for (III) , (V) , (XVI) to (XXVIII) , (XXXVI) and (XXXVII) are generic formulas and embrace a wide range of actual compounds. The ability of such individual compounds to form active polymerizations catalysts, and the actual activity of those catalysts, will be dependent on the structure of the individual compound used, and the circumstances under which it is used. For instance, whether such a compound will be active and how active it will be will be dependent to some extent on its actual structure, and particularly how that structure affects the steric and electronic properties of the compound as a ligand on nickel . If there lε too much or too little steric hindrance about the group that actually coordinates to the nickel atom, the compound may be ineffective. Similarly, if the group that actually coordinates to the nickel is made too electron rich or poor, the compound may be made ineffective. Thiε may be illuεtrated by the following list of compounds, which were ineffective in catalyzing the polymerization of ethylene under the conditions described for Examples 23-66. The specific compounds are: However, as mentioned above these compounds failed under a specific set of conditions. If one peruses through the Examples herein, one will find that certain of these compounds may fail to promote polymerization by one method, while be active in another methoα, and/or one finds the yield of polymer may change significantly under different conditions Therefore failure in any particular polymerization process doesn't mean failure in all Conditions in such procesεes may be varied, for instance the ^ pressure temperature and solvent used The polymerizations may be carried out in slurry, solution or the gas phase, in continuous, semi-batch or batch reactors In addition, the particular starting form of the (proto) catalyst system may affect reactivity For instance, differences may be found when using 0 (II) as a starting material than when using a preformed π-allyl complex Determining the activity of any particular compound which is described herein is relatively easy The compound may be used n any of the polymerization systems described herein, and if needed *> the conditions, such as temperature and preεεure, may be varied Particularly for polymerizationε m which the active nickel catalyst lε formed n situ, it may be important that the catalyst components all be soluble, at least initially, so solvent selection may be important Such experiments are simple and quick 0 to run ana don't involve much experimentation It is alεo noted that some forms of (XXXIII) may be prepared by other methoαs known in the art, see for instance copending U S Application Number 08/590,650, filed January 24, 1996 (CR9608D) which lε hereby included by reference 5 In all of the polymerization processes and polymerization catalystε herein it is preferred that one or more of the following not be significantly present an organoalummum compound, an aluminum halide any other transition metals, especially titanium and/or zirconium, reducing agents, especially metal or metalloid 0 hydrides, and any organometalic compound except for nickel compounds By not significantly present is meant there is not enough present to affect the course of the polymerization It is more preferred that one or more of these be absent from a polymerization process and/or polymerization catalyst, except for 5 normal impurities It is also preferred that a polymerization catalyst or catalyst system for a polymerization process herein consist essentially of the stated ingredients. In all of the nickel complexes herein, except those specifically enumerated as nickel [0] complexes, it is preferred that the nickel be in the +2 oxidation state. In the Exampleε the following abbreviations are used: BAF - {tetrakiε [3, 5-bis (trifluoromethyl)phenyl]borate} Bu - butyl COD - η -l, 5-cyclooctadiene Cy - cyclohexyl DSC - differential scanning calorimetry Et- ethyl Me - methyl Ph - phenyl (C 6 H 5 -) RT - room temperature Tg - glasε tranεition temperature THF - tetrahydrofuran TLC - thin layer chromatography Tm - melting point In the Exampleε, all ethylene pressures are gauge pressures unless otherwise noted. The formulas given for the nickel complexes of εpecific ligandε in the Exampleε may not be accurate and are for illuεtration purpoεeε only. They represent the best estimate of the structure (or one of several possible structures) based on available data. Example i Under a nitrogen atmosphere, Ni (COD) 2 (0.017 g, 0.06 mmol) and compound (VI) (0.023 g, 0.06 mmol) (purchased from the SALOR fine chemical division of Aldrich Chemical Co.) were dissolved in benzene (5.0 mL) To the resulting solution was added HBAF" (Et 2 0)2 (0.060 g, 0.06 mmol) . The resulting solution was immediately frozen inside a 40 mL shaker tube glass insert. The glass insert was tranεferred to a shaker tube, and ltε contentε allowed to thaw under an ethylene atmosphere. The reaction mixture waε agitated under 6.9 MPa C 2 H 4 for 18 h at 25°C. The final reaction mixture contained polyethylene, which waε washed with methanol and dried; yield of polymer = 9.1 g. 1 H NMR (CDCI2CDCI 2 , 120°C) showed that this sample contained 90 methyl- ended branches per 1000 methyleneε. Two melting points were observed by differential scanning calorimetry: a very broad melting point centered at approximately 0°C, and a sharp melting point at 115°C. (VI) Example 2 Under a nitrogen atmosphere, Ni (COD) 2 (0.017 g, 0.06 mmol) and compound (VII) (0.023 g, 0.06 mmol) were dissolved in benzene (5 0 rr To the resulting solution waε added HBAF (Et 2 0) 2 (0.060 g, 0.06 mmol) . The resulting solution was immediately frozen mεiαe a 40 mL shaker tube glasε insert. The glass insert was transferred to a shaker tube, and its contents allowed to thaw under an ethylene atmoεphere. The reaction mixture waε agitated under 6.9 MPa C2H 4 for 18 h at 25°C. The final reaction mixture contained polyethylene, which was filtered off, washed with methanol and dried; yield of polymer = 4.9 g. By 1 H NMR integration it was shown that th s material was branched polyethylene containing 109 methyl-ended branches per 1000 methylenes. 1 H NMR (CDCI3) d 1.24 (s, methylene and methine protonε) , 0.82 (d, methyls). (VII) Example 3 Under a nitrogen atmosphere, Ni(COD)2 (0.017 g, 0.06 mmol) and compound (VIII) (0.024 g, 0.06 mmol) were dissolved in benzene (5.0 L) . To the resulting solution was added HBAF ' (Et2θ) 2 (0.060 g, 0.06 mmol; . The resulting solution was immediately frozen inside a 40 mL shaker tube glass insert. The glass insert was transferred to a shaker tube, and its contents allowed to thaw under an ethylene atmosphere. The reaction mixture was agitated under 6.9 MPa C2H 4 for 18 h at 25°C. The final reaction mixture contained polyethylene, which was filtered off, washed with methanol and dried; yield of polymer = 0.26 g. 1 H NMR (C6D3CI3, 120°C) showed that this sample contained 18 methyl-ended branches per 1000 methyleneε. (VIII) Example 4 Under a nitrogen atmosphere, Ni(COD) 2 (0.017 g, 0.06 mmol) and compound (IX) (0.020 g, 0.06 mmol) were dissolved in benzene (5.0 mL) . To the resulting solution was added HBAF'(Et 2 0)2 (0.060 g, 0.06 mmol) . The resulting solution was immediately frozen inside a 40 mL shaker tube glass insert. The glass insert was transferred to a shaker tube, and its contents allowed to thaw under an ethylene atmosphere. The reaction mixture was agitated under 6.9 MPa C2H4 for 18 h at 25°C. The final reaction mixture contained polyethylene, which was washed with methanol and dried; yield of polymer = 0.73 g. T m = 126.9°C (second heat) as determined by DSC. 1 H NMR (CDC1 2 CDC1 2 , 25°C) showed that this sample contained approximately 7 methyl-ended branches per 1000 methylenes. (IX) Example 5 Under a nitrogen atmosphere, Ni (COD) 2 (0.017 g, 0.06 mmol) and compound (X) (0.030 g, 0.06 mmol) were dissolved in benzene (5.0 L) . To the resulting solution was added HBAF (Et2θ>2 (0.060 g, 0.06 mmol) . The resulting solution was immediately frozen inside a 40 mL shaker tube glass insert. The glaεε insert was transferred to a shaker tube, and its contents allowed to thaw under an ethylene atmosphere. The reaction mixture was agitated under 6.9 MPa C2H 4 for 18 h at 25°C. The final reaction mixture contained polyethylene, which was washed with methanol and dried; yield of polymer = 1.40 g. Tπ, = 123.6°C as determined by DSC. 1 H NMR (CDCI 2 CDCI 2 , 120°C) showed that this sample contained approximately 10 methyl-ended branches per 1000 methylenes. Example 6 Under a nitrogen atmosphere, Ni(COD)2 (0.017 g, 0.06 mmol) and compound (XI) (0.029 g, 0.06 mmol) were dissolved in benzene (5.0 mL) . To the resulting solution was added HBAF " (Et 2 0)2 (0.060 g, 0.06 mmol) . The resulting solution waε immediately frozen inside a 40 mL shaker tube glass insert. The glass insert waε transferred to a shaker tube, and its contents allowed to thaw under an ethylene atmosphere. The reaction mixture was agitated under 6.9 MPa C2H 4 for 18 h at 25°C. The final reaction mixture contained polyethylene, which was filtered off, washed with methanol and dried; yield of polymer = 0.43 g. 1 H NMR (CDCI2CDCI2, 120°C) showed that thiε sample contained 19 methyl-ended branches per 1000 methylenes. (XI) Example 7 Under a nitrogen atmosphere, Ni(COD>2 (0.017 g, 0.06 mmol) and 2,6-diisopropylaniline (0.011 g, 0.06 mmol) were dissolved in benzene (5.0 L) . To the resulting solution waε added HBAF'(Et2θ)2 (0.060 g, 0.06 mmol) . The resulting solution waε immediately frozen inside a 40 mL shaker tube glass insert. The glass insert was transferred to a shaker tube, and its contents allowed to thaw under an ethylene atmosphere. The reaction mixture was agitated under 6.9 MPa C2H 4 for 18 h at 25°C. The final reaction mixture contained polyethylene, which was filtered off, washed with methanol and dried; yield of polymer = 0.72 g. Trn = 121.3°C (second heat) as determined by DSC. ^-H NMR (C6D3CI3, 120°C) showed that this sample contained 26 methyl-ended brancheε per 1000 methyleneε. Another experiment run under identical conditionε afforded 0.17 g of polymer,- three other experimentε in which 0.12 mmol of 2,6-diisopropylaniline were employed (other conditions the same as above) afforded 0.30 g, 0.20 g, and 0.64 g of polymer. Example 8 Under a nitrogen atmosphere, Nι(COD)2 (0.017 g, 0.06 mmol) and 2,6-dιethylanιlme (0.018 g, 0.12 mmol) were dissolved in benzene (5.0 mL) To the resulting solution was added HBAF (Et 2 0) 2 (0.060 g, 0.06 mmol) . The resulting solution was immediately frozen inside a 40 mL shaker tube glaεε insert. The glass insert was transferred to a shaker tube, and its contentε allowed to thaw under an ethylene atmosphere. The reaction mixture waε agitated under 6.9 MPa C2H4 for 14 h at 25°C. The final reaction mixture contained polyethylene, which was filtered off, waεhed with methanol and dried; yield of polymer = 0.34 g. T m = 122.5°C (second heat) as determined by DSC. Example 9 Under a nitrogen atmosphere, Ni (COD) 2 (0.017 g, 0.06 mmol) and aniline (0.011 g, 0.12 mmol) were dissolved in benzene (5.0 mL) To the resulting solution was added HBAF (Et 2 0) 2 (0.060 g, 0.06 mmol) . The resulting solution waε immediately frozen inside a 40 mL εhaker tube glaεε insert. The glass insert waε transferred to a εhaker tube, and its contents allowed to thaw under an ethylene atmosphere. The reaction mixture was agitated under 6.9 MPa C 2 H 4 for 14 h at 25°C. The final reaction mixture contained polyethylene, which was filtered off, washed with methanol and dried, yield of polymer = 0.049 g T m = 112.0°C as determined by differential scanning calorimetry. Example 1Q Under a nitrogen atmosphere, Nι(COD)2 (0.017 g, 0.06 mmol) and 1, 8-dιammonaphthalene (0.010 g, 0.06 mmol) were dissolved in benzene (5.0 mL) . To the resulting solution waε added HBAF (Et 2 0) 2 (0.060 g, 0.06 mmol) . The resulting solution was immediately frozen inside a 40 mL shaker tube glass insert. The glass insert was transferred to a shaker tube, and its contents allowed to thaw under an ethylene atmosphere. The reaction mixture waε agitated under 6.9 MPa C 2 H4 for 18 h at 25°C. The final reaction mixture contained polyethylene, which was washed with methanol and dried; yield of polymer = 5.38 g. DSC on this sample showed a very broad melting point, T m = 37.0°C (second heat) . Example 11 Under a nitrogen atmosphere, Nι(COD) 2 (0.017 g, 0.06 mmol) and compound (XII) (0.016 g, 0.12 mmol) were dissolved in benzene (5.0 mL) To the resulting solution was added HBAF (Et θ) 2 (0.060 g, 0 06 mmol) The resulting solution was immediately frozen inside a 40 mL shaker tube glass insert. The glass insert waε tranεferred to a shaker tube, and its contents allowed to thaw under an ethylene atmosphere The reaction mixture was agitated under 6.9 MPa C2H 4 for 18 h; during this time the temperature inside the reactor varied between 25 and 33°C . The final reaction mixture contained polyethylene, which was filtered off, washed with methanol and dried; yield of polymer = 0.13 g. T m = 119.3, 129 0°C as determined by DSC. (XII) Example 12 Under a nitrogen atmosphere, Ni(COD) 2 (0 017 g, 0.06 mmol) and ortho-phenylenediamme (0.013 g, 0.12 mmol) were dissolved n benzene (5 0 mL) To the resulting solution was added HBAF (Et 2 0) 2 (0 06 ° 9- ° 06 mmol) The resulting solution was immediately frozen inside a 40 L shaker tube glass insert The glass insert was transferred to a shaker tube, and its contents allowed to thaw under an ethylene atmosphere The reaction mixture was agitated under 6.9 MPa C 2 H 4 for 18 h at 25°C. The final reaction mixture contained polyethylene, which was filtered off, washed with methanol and dried; yield of polymer = 0.052 g. T m = 98 0, 119.0°C as determined by DSC. Example 13 Under a nitrogen atmosphere, Ni (COD) 2 (0.017 g, 0.06 mmol) and compound (XIII) (0.013 g, 0.06 mmol) were dissolved in benzene (5.0 mL) To the resulting solution was added HBAF (Et2θ) 2 (0.060 g, 0.06 mmol) The resulting solution was immediately frozen inside a 40 mL shaker tube glass insert. The glasε insert was transferred to a shaker tube, and its contents allowed to thaw under an ethylene atmosphere. The reaction mixture was agitated under 6.9 MPa C2H4 for 18 h at 25°C. The final reaction mixture contained polyethylene, which was filtered off, washed with methanol and dried; yield of polymer = 0.76 g. (XIII) Example .14 Under a nitrogen atmosphere, Nι(C0D)2 (0.017 g, 0.06 mmol) and compound (XIV) (0.030 g, 0.06 mmol) were dissolved in benzene (5 0 L) To the resulting solution was added HBAF (Et2θ)2 (0.060 g, 0.06 mmol). The resulting solution was immediately frozen insiαe a 40 mL shaker tube glass insert The glaεε insert waε transferred to a shaker tube, and its contentε allowed to thaw undei an ethylene atmosphere. The reaction mixture waε agitated under 6 9 MPa C2H 4 for 18 h; during thiε time the temperature inside the reactor varied between 25 and 33°C . The final reaction mixture contained polyethylene, which waε filtered off, waεhed with methanol and dried, yield of polymer = 0.039 g. T m = 126 2 C C as determined by DSC (XIV) Example 15 Under a nitrogen atmosphere, Ni(COD) 2 (0.017 g, 0.06 mmol) and anthranilic acid (0.008 g, 0.06 mmol) were dissolved m benzene (5.0 mL) . To the resulting solution was added HBAF (Et 0) (0.060 g, 0.06 mmol) . The resulting solution waε immediately frozen inside a 40 mL shaker tube glass insert. The glasε insert was transferred to a shaker tube, and ts contentε allowed to thaw under an ethylene atmosphere. The reaction mixture was agitated under 6.9 MPa C 2 H4 for 18 h; during this time the temperature inside the reactor varied between 25 and 39°C. The final reaction mixture contained polyethylene, which waε filtered off, washed with methanol and dried; yield of polymer = 1.74 g T m = 118.4°C as determined by DSC. Example 16 Under a nitrogen atmosphere, Ni(C0D) 2 (0.017 g, 0.06 mmol) and compound (XXXVIII) (0.008 g, 0.06 mmol) were dissolved in benzene (5.0 mL) . To the resulting solution was added HBAF (Et 2 0) 2 (0.060 g, 0.06 mmol) . The resulting solution was immediately frozen inside a 40 mL shaker tube glasε insert. The glasε insert waε transferred to a shaker tube, and its contentε allowed to thaw under an ethylene atmosphere. The reaction mixture was agitated under 6.9 MPa C2H 4 for 18 h; durmg this time the temperature inside the reactor varied between 25 and 34°C. The final reaction mixture contained ' polyethylene, which waε filtered off, washed with methanol and dried; yield of polymer = 1.20 g Tm = 120.2, 132.3°C as determined by DSC. (XXXVIII) Example 17 Synthesis of (VII) 2,6-dιιsopropylanilme (17.7 g, 100 mmol), 1,2-dibromoethane (9.4 g, 50 mmol), and diisopropylethylamme (20 mL) were heated to reflux for 2 days. Excess diisopropylethylamme was removed from the white crystals in vacuo, and the residue was washed with CH2C1 2 . The CH Cl was evaporated to give a red-brown residue. The crude product was recrystallized from methanol to afford white crystals of (VII) . Exampl 18 Synthesiε of (IX) 2, 6-Dιιεopropylanilme (0.89 g, 5.0 mmol) and pentafluorobenzaldehyde (0.98 g, 5.0 mmol) were diεεolved in CH2CI2 (20 mL) and the reaction mixture was stirred overnight at room temperature. The solvent was removed m vacuo to afford 1.5 g of (IX) as an off-white solid. Example 19 Synthesis of (X) 1, 1 ' -Biphenyl-2,2 ' -diylphosphorochloridite (0.251 g, 1.0 mmol) was disεolved in anhydrouε diethyl ether (15 mL) under nitrogen. To this stirred solution was slowly added the sodium salt of salιcylaldehyde-2, 6-diisopropylanilineimine (0.303 g, 1.0 mmol) . The solution was stirred for one hour, and then filtered. The filtrate was evaporated to afford a yellow oil. The oil waε rediεsolved m approximately 3-4 mL petroleum ether, Slow evaporation of the εolution at room temperature gave yellow cryεtalε of (X) . 1 H NMR (CDCI3) d 8.55 (ε, 1H, N=CH) , 8.25 (d, 1H, Haryl' ■ 7.50-7.05 (mult, 15H, H a ryl) . 2.95 (sept, 2H, CHMe2) , 1.15 (d, 12K CHMe ) ; 31 P NMR (CDCI3) d 142.44. 1,1' -bιphenyl-2, 2 ' -diylphosphorochloridite εalιcylaldehyde-2, 6-diisopropylanilineimine sodium salt The preparation of 1, 1 ' -biphenyl-2,2 ' - diylphosphorochloridite can be found in the following references : WO 9303839, U.S. Patents 4,769,498, and 4,688,651, and Cuny, G.D., et al., J. Am. Chem . Soc . vol. 115, p. 2066 (1993) . Salιcylaldehyde-2,6-dιιsopropylanilmeιmme was prepared by stirring an equimolar mixture of salicylaldehyde and 2,6- dnεopropylanilme the presence of a catalytic amount of formic acid in metnanol for several days at room temperature; the product waε from pentane at -78°C. The sodium salt was prepared by reaction with sodium hydride in THF. Example 20 Synthesis of (XI) Compound (X)I was prepared by the method of Example 19 from 6-chloro-6H-dιbenz [c,e] [1,2]oxaphosphorin and the sodium salt of salicylaldehyde-2,6-dιιsopropylanilιneιmme. -*-H NMR (CDCI3) d 8.20-7.00 (mult, 16H, N=CH and H ar y_) , 2.80 (sept, 2H, CHMe 2 ) , 1.03 (overlapping d's,CH e 2 , 12H) ; 31 P NMR (CDCI3) d 128.8ppm. 6-Chloro-6H-dιbenz [c,e] [1, ]oxaphosphorin 6-Chloro-6H-dιbenz [c,e] [1,2]oxaphosphorin was prepared according to a published procedure: Pastor, S.D., et al. , Pnoεphoruε and Sulfur vol. 31, p. 71 (1987) . Example 21 Synthesis of (XIV) 1, 1 ' -biphenyl-2, ' -diylphosphorochloridite (0.125 g, 0.50 mmol) waε diεεolved in 15 mL 1.1 anhydrouε ether/tetrahydrofuran under nitrogen To this εtirred solution waε added the εodium salt of N- (ortho-hydroxy)benzyl-2,6-dnsopropylaniline (0.153 g, 0.50 mmol) . Stirring was continued for another 5.5 hourε before the εolution waε filtered. Evaporation of the filtrate afforded a nearly colorleεs oil. This material was redissolved in diethyl ether/petroleum ether (-1:2), and the solution cooled to -40°C. A small amount of material precipitated from the solution and was removed Slow evaporation of the solution afforded white crystals of compound XIV 1 H NMR (CDCI3) d 7.60-7.00 (mult, 15H, H ary ι) , 4 05 (ε, 2H, CH 2 ), 3.40ppm (br ε, 1H, NH) , 3.25 (sept, 2H, CHMe 2 ); 1.10 (d, 12H, CH e2) N- (ortho-hydroxy)benzyl-2,6-dιιsopropylanιlme sodium salt N- (ortho-hydroxy)benzyl-2,6-dnsopropylanιlme was prepared by NaEr. 4 reduction of εalιcylaldehyde-2, 6-dιιsopropylanιlιneιmme in CH3OH/CHCI 3 (chloroform was added to help solubilize the aniline starting material) . The sodium salt of this compound was prepared by reaction with sodium hydroxide in tetrahydrofuran. Example 22 Synthesis of (VIII) Compound (VIII) was prepared by reduction of N- (ortho- dιιεopropylphoεphmoxy)benzyl-2,6-dιιsopropylanιlmeιmme with 2 equivalentε of 1-BU2AIH in toluene at 0°C, followed by warming to room temperature and a baεic workup N- ιortho-dι sopropylphosphmoxy) benzyl-2 , 6-dιιsopropylanιlιneιmιne N- (ortho-dnsopropylphosphmoxy) benzyl-2 , 6- diisopropylanilmeimme was prepared by reaction of salιcylaldehyde-2 , 6-dιιsopropylanilιne mιne with chlorodnsopropylphosphme and triethylam e in toluene at room temperature Exampleε 23-66 These Examples were all done by the same general procedure. Under a nitrogen atmosphere, Ni (COD) 2 (0.017 g, 0.06 mmol) and the ligand to be tested (0.06 or 0.12 mmol) were dissolved m benzene (5 0 mL) To the resulting solution was added HBAF (Et 2 θ) 2 (0.060 g, 0 06 mmol The resulting solution inside a 40 mL shaker tube glass insert waε immediately frozen in a freezer inside the glove box The glasε insert waε transferred to a shaker tube, and its contents allowed to thaw under an ethylene atmosphere of 6.9 MPa. The reaction mixture was agitated under 6.9 MPa of ethylene preεεure for about 18 h Any polyethylene m the final reaction mixture was washed with methanol and dried. Melting points of some of the polymers were determined by DSC. These (when determined) along with polymer yields and other data are given in Table 1 Tne structures of the ligands (except if already shown abovej are listed after Table 1 52 61 67 68 70 71 10 Examples 67-77 Norbornene Polymerization General procedure: The reactionε were carried out in a dry, deoxygenated atmosphere The catalyst waε weighed into a 20 ml glass scintillation vial and a stir bar waε added A εolution of dry dichloromethane/norbornene (3 ml, 43 maεε % norbornene) waε added and the resulting solutions stirred for 20-90 h. Each product was added to stirring methanol (m air) to precipitate the polymer. The polymer was filtered, washed with methanol/10% HCI solution and methanol and finally dried under vacuum. In each case purity was improved by redissolvmg the polymer in chloroform and reprecipitatmg with methanol. 1 H-NMR (CDCI3) confirmed that the products were addition polymers of norbornene Details and results of these polymerization are given Table 2. Structures of the catalvsts used are shown after Table 2 Table 2 E End groups visible in 1 H NMR of polymer indicate lower molecular weight 102 Examples 78-85 Styrene Polymerization General procedure: The reactions were carried out in a dry, deoxygenated atmosphere. The nickel containing catalyst waε weighed into a 20 ml glass scintillation vial and a stir bar added Dry dichloromethane (2 ml) followed by styrene (2 ml, filtered through alumina, phenothiazine inhibitor) waε added and the resulting solutions shaken in the dark for 20 h The products were added to stirring methanol (in air) to precipitate the polymer The polymer was filtered, washed with methanol/10% HCI solution and methanol and finally dried under vacuum. Polymers were characterized using 13 C-NMR (CDCI3) which indicated that in each case the product waε enriched in racemic diad units relative to atactic polyεtyrene [for measuring tacticities of polystyrenes see T Kawamura, et al , Macromol. Rapid Commun., vol. 15, p 479- 486 (199*» j Details of each polymerization and resultε are shown m Tabxe 3 Structureε of catalysts are shown after Table 2, above Table 3 Examples 86-94 Styrene/Norbornene Copolymer zat.ππ General procedure. The reactions were carried out in a dry, deoxygenated atmosphere The catalyst was weighed into a 20 ml glasε scintillation vial and dry dichloromethane (l ml) and a stir bar added A solution of dry dichloromethane (2 ml) , styrene (2 ml, Aldrich Chemical Co , 99+%, filtered through alumina, phenothiaz e inhibitor added) and 1.5 g norbornene (Aldrich Chemical Cc , 99%) was added and the resulting solutions shaken m the dark for 20 h The products were added to stirring methanol (in air) to precipitate the polymer The polymer was filtered, washed with methanol/10% HCI solution and methanol and finally dried under vacuum •• ■ H-NMR(CDC1 3 ) indicated that in each case the product contained both styrene and norbornene The absence of a resonance between 6 2 and 6 7 ppm (assigned to the ortho protons in chains of polyεtyrene) confirms that the product is a copolymer [see for instance A Benaboura, et al. , CR. Acad. Sc Paris, Ser 2, vol. 3C1, p 225 (1985)] The absence of a polystyrene Tg in the DSC confirmed that the products are copolymers Details and results of these polymerization are found in Table 4 Structures of the nickel containing catalystε are εhown after Tacle 2, above Table .4 Examples 95 - 1Q7 Following the procedure of Exampleε 23 - 66, ethylene waε polymerized. The resultε are reported in Table 5. The structures of the ligands are listed after Table 5. Table 5 111 112 113 114 Examples 108-183 General Synthesis of Nickel Allyl Initiators. A mixture of one to two equiv of the appropriate ligand, one equiv of NaBAF, and 0 5 eσuiv of [ (allyl)N (m-X) ] 2 (X = Cl or Br) waε dissolved in Et 2 C The reaction mixture was stirred for several h before being filtered The solvent was removed in vacuo to yield the desired product (The [ (allyl)Ni (m-X) ] 2 precursors were synthesized according to the procedures published in the following reference Wilke, G , et al . , Angew. Chem . Int . Ed. Engl . 1996, 5, 151 - 164 ) The following X H and 13 C spectroscopic assignments of the BAF counterion in CD C1 2 were invariant for different complexes and temperatures and are not repeated the spectroscopic data for eacn of the cationic allyl complexes- [3, 5-C6H3- (CF3) 2 ] 4 " (BAF 1 H NMP (CD 2 C1 2 ) d 7 74 (s, 8, H D ) , 7 57 (ε, 4, H p ) , 13 C NMR (CD 2 C1 2 ) d 162 2 (q, JcB = 37.4, C lpso ) , 135 2 (C 0 ) , 129 3 (q, J CF = 31 3, Cm), 125 0 (q, J C F = 272.5, CF3), 117 9 (C p ) General Procedure for the Screening of Ethylene Polymerization by Nickel Allyl Initiators. In the drybox, a glass insert waε loaded with the isolated allyl initiator synthesized by the above general procedure The insert was cooled to -35°C in the orybo> freezer, 5 mL of solvent (typically ξOς, or CDCI3) waε added to the cold insert, and the insert waε then capped and sealeα Outside of the drybox, the cold tube waε placed under 6 9 MPa of etnylene and allowed to warm to RT aε it was shaken mechanically for approximately 18 h An aliquot of the solution waε useα to acquire a -*-H NMR spectrum The remaining portion was addeo to - 20 mL of MeOH in order to precipitate the polymer The polyethylene waε lεolated and dried under vacuum Example 1Q8 The general synthesis of nickel allyl initiators was followed using 64 mg of ligand, 53 mg of [(C 3 H5) ι(μ-Cl)]2, and 347 mg of NaBAF A wheat yellow powder (307 mg) was isolated. -*-H and 13 c NMR spectra are consistent with the above structure with one equiv of Et 2 0 present. In particular, at -80°C two sets of ammo proton resonances are observed and are coupled to each other This is consistent with the above structure m which both nitrogen atomε are bound to nickel. At room temperature (20°C , one broad resonance is observed at 5.64 pp for all of the ammo protons- 1 H NMR (CD CI2, 300 MHz, -80°C) d 7.81 (d, 2 , J = 8.09, H 0 or H p ) , 7.41 (t, 2, J = 8.1, H m ) , 7.26 (d, 2, J = 6.74, H 0 or H p ) , 5.49 (m, 1, J = 6.7, H CCHCH 2 ) , 5.43 (d, 2, J = 10.8, NHH') , 5.04 (d, 2, J = 12.14, NHH') , 3.38 (br q, 4, J = 6.7, 0(CH 2 CH 3 ) 2 ) , 3.26 (d, 2, J = 6.8 (HH'CCHCHH' ) , 2.17 (d, 2, J = 13.5, HH'CCHCHH 1 ) , 0.92 (t, 6, J = 6.1, 0(CH 2 CH3) 2 ) ; 13 C NMR (CD 2 C1 2 , 75 MHz, rt) d 136.1, 130.4, 129.0, 126.7, 123.2 and 121.7 (C ary ι) , 115.4 (H 2 CCHCH 2 ) , 65.9 (H 2 CCHCH 2 ) , 55.7 (O(CH 2 CH 3 ) 2 ) , 14.9 ( 0 ( CH 2 CK 3 )2 ) • Example 109 The allyl initiator of Example 108 was uεed to polymerize ethylene n CDCI3 at RT according to the general polymerization procedure using 24 mg of catalyst. Polyethylene waε isolated (304 mg 11 . Example 11 Q The general synthesis of nickel allyl initiators was followed using 151 mg of ligand, 205 mg of [ (H2CCHCHPh)Nι (μ-Cl) ] 2 , and 860 mg of NaBAF. A yellow-brown powder (694 mg) was isolated. The 1 H NMR spectrum indicates that one equiv of Et 2 0 is present. The spectrum, particularly the observation of 4 inequivalent coupled ammo protons, is consistent with the above structure in which both nitrogen atoms are bound to nickel. The amino resonanceε remain inequivalent at leaεt up to 60°C: 1 H NMR (CD 2 C1 , 300 MHz, -40°C) d 7.85 - 7.25 ( , 10, H ar y]_) , 6.47 (d, 1, J = 6.8, Haryl) . 6 -° 3 (t of d, 1, J = 12.8, 7.2, H 2 CHCHPh) , 5.17 (d, 1, J = 10.8, NHH") , 4.89 (d, 1, J = 10.8, NHH') , 4.23 (d, 1, J = 12.1, N'HH'), 3.73 (d, 1, J = 12.1, H 2 CHCHPh) , 3.66 (d, 1, J = 10.8, N'HH'), 3.41 (q, 4, J = 7.2, 0(CH 2 CH 3 ) 2 ), 3.34 (d, 1, J = 6.8, HH'CHCHPh) , 2.31 (d, 1, J = 12.1, HH'CCHCHPh) , 1.05 (t, 6, J = 7.4, 0(CH 2 CH3 ) ) • Example 11 The allyl initiator of Example 1110 waε uεed to polymerize ethylene in CβDg at 80°C according to the general polymerization procedure using 67 mg of catalyst. No polyethylene was isolated under these conditions. However, the 1 H NMR spectrum of the reaction mixture indicated that butenes and higher olefmε were produced in significant amounts. Example 112 Tne general synthesis of nickel allyl initiators waε followed using 202 mg of ligand, 127 mg of [ (C 3 Hs)Nι (μ-Cl) ]2 • and 82S mg of NaBAF A yellow-orange powder (967 mg) was isolated. The NMR spectra are consiεtent with the εtructure shown above, in which both nitrogen atomε coordinate to nickel. 1 H NMR (CD2CI2, 300 MHz, rt) d 7.83 (d of d, 2, J = 5.9, 3.3, H m ) , 7.56 (ε, 2, H D or H p ) , .54 (d, 2, J = 2 9, H σ or H p ) , 6.10 (t of t, 1, J = 13.4, 7.1, H 2 CCHCH 2 ) , 3.23 (d, 2, J = 7.3, HH'CCHCHH') , 3.1 (br, 12, 2 x NMe 2 ) , 2.58 (d, 2, J = 13.2, HH'CCHCHH') ; 13 C NMR (CD 2 C1 2 , 75 MHz, rt, nonaromatic carbonε only) d 117.6 (H2CCHCH2) , 60.2 (H 2 CCHCK 2 J, 55.1 (br, NMe ) . Example 113 The allyl initiator of Example 112 was used to polymerize ethylene in CDCI3 at RT according to the general polymerization procedure (with the exception that 4.1 MPa of ethylene was used) using 40 mg of catalyst. Polyethylene waε not isolated. The 1 H NMR spectrum showed the production of butenes and a small amount of higher olefinε. Example 114 The general εynthesiε of nickel allyl initiatorε waε followed using 103 mg of ligand, 100 mg of [ (H2CCHCMe2) i(μ-Br)] ■ and 427 mg of NaBAF. A pale pink powder (517 mg) waε isolated. The NMR spectrum iε consistent with the structure shown above, in which both nitrogen atoms coordinate to nickel. 1 H NMR (CD2CI2, 300 MHz, rt) d 8.2 - 7.4 (m, 6, H ary ι) , 5.33 (dd, 1, J = 12.8, 7.4, H 2 CCHCMe2) , 3.35 - 2.80 (br, 12, N eMe' , N'MeMe'), 2.78 (dd, 1, J = 8.1, 2.7, HH'CHCMe 2 ), 1.75 (dd, 1, J = 13.5, 2.7, HH'CHCMe2) , 1.22 and 0.73 (ε, 3 each, H 2 CCHCMeftfe') . Example 115 The allyl initiator of Example 114 was used to polymerize ethylene CDCI3 at RT according to the general polymerization procedure using 66 mg of catalyst. Polyethylene was isolated (23 mg) . Example 11s The allyl initiator of Example 114 was used to polymerize ethylene in CDCl 3 at 80°C according to the general polymerization procedure using 62 mg of catalyst. No polyethylene was isolated; however, the 1 H NMR spectrum of the reaction mixture showed the production of buteneε, higher olefins, and a broad (CH 2 )n peak at 1.25 pp Example 117 The general εynthesiε of nickel allyl initiators was followed using 135 mg of ligand, 48 mg of [ (C 3 Hs)Ni(μ-Cl)] 2 , and 307 mg of NaBAF. A yellow powder (394 mg) was isolated. The 1 H and 13 C NMR spectra are consistent with both nitrogen atoms coordinating to nickel, as shown above, with the aryl rings lying trans to each other in the majority of the product. Other isomers may be present lesser amounts: -*-H NMR (CD2CI2, 300 MHz, -40°C) d 7.4 - 7.0 (m, 6, H ary ι) , 5.68 (m, 1, H2CCHCH2) , 5.53, 5.38, 4.84 and 4.22 ( , 1 each, NCHH'C'HH'N' ) , 3.4 - 2.8 (m, 6, NH, N'H, CHMe 2 , C'HMe 2 , C' 'HMe 2 , C , , 'HMe2), 2.73 (d, 1, J = 6.7, HK'CCHCHH'), 2.62 (d, 1, J = 6.8, HH'CCHCHH'), 2.39 (d, 1, J = 13.5, HH'CCHCHH'), 1.55 (d, 1, J = 13.5, HH'CCHCHH'), 1.8 - 1.2 (d, 3 each, CHMeMe', C'H eΛfe', C'HMeMe', C' ' 'HMeMe') ; 13 C NMR (CD C1 2 , 75 MHZ, rt) d 140.9, 140.8, 139.9, 139.4, 138.9 and 138.4 (Ar: C lpso , C 0 , C 0 ' and Ar 1 : Ci pso , C 0 , C 0 '), 129.0, 128.8, 127.1, 127.0, 125.4 and 125.1 (Ar: C m , Cm', C p and Ar' : C m , C m ' , C p ) , 116.1 (H2CCHCH2) , 60.7, 55.9, 54.3 and 53.0 (H2CCHCH2, NCH2CH2N'), 31.7, 30.5, 30.0 and 29.4 (CHMe2, C'HMe 2 , C'HMe 2 , C''HMe2), 26.4, 26.0, 24.4, 24.2, 24.2, 24.2, 24.0 and 22.9 (CHMeMe', C'HMeMe', C'HMeMe', C ' 'HMeMe') . The allyl initiator of Example 117 waε used to polymerize ethylene in CgDg at 80°C according to the general polymerization procedure using 63 mg of catalyst. Polyethylene (3.49 g) waε isolated. 1 H NMR spectrum of the isolated polymer indicates the formation of branched polyethylene with roughly 100 methyl branches per 1000 carbon atomε. Example ιi9 The allyl initiator of Example 117 was used to polymerize ethylene in CDCl 3 at 80°C according to the general polymerization procedure using 68 mg of catalyst. Polyethylene (1.69 g) waε isolated. Example 120 The general synthesis of nickel allyl initiators waε followed using 106 mg of ligand, 53 mg of [ (C 3 Hs)Ni (μ-Cl) ] 2 , and 349 mg of NaBAF. A yellow powder (394 mg) was isolated. The 1 H and 13 C NMR spectra are consistent with both nitrogen atoms coordinating to nickel, as shown above, with the aryl rings lying tranε to each other in the majority of the product. Other isomers may be present in lesser amounts: 1 H NMR (CD CI2, 300 MHz, rt) d 8.3 - 7.2 (m, 10, H ary l) , 5.9 (m, 1, H 2 CCHCH 2 ) , 3.9 - 2.8 (m, 10, HH'CCHCHH', NCH 2 CH 2 N\ NCH 2 CH 3 , N'CH 2 CH 3 ), 2.49 (d, 1, J = 13.6, HH'CCHCHH') , 2.15 (d, 1, J = 13.6, HH'CCHCHH'), 1.36 and 1.17 (t, 3 each, J = 7.2, NCH2CH3 and N'CH CH3); 13 C NMR (CD 2 C1 2 , 75 MHz, rt) d 150.1 and 147.5 (Ph: Ci pso and Ph': Ci pso ) , 130.8, 130.8, 130.8, 130.7, 129.2, 128.9, 128.2, 124.0, 123.9 and 122.6 (Ph: C 0 , C 0 X C m , C m ' and C p ; Ph' : C 0 , C 0 ', C m , C m ' and C p ) , 115.6 (H CCHCH 2 ) , 59.6, 58.7, 58.3, 57.9, 57.3 and 56.4 (H2CCHCH2, NCH 2 CH 3 , N'CH CH 3 , CH2CH2N' ) , 12.6 and 11.8 (NCH 2 CH 3 and N'CH 2 CH 3 ) . Example 121 The allyl initiator of Example 120 was used to polymerize ethylene CDC1 3 at 60°C according to the general polymerization procedure using 25 mg of catalyst. A few mg'ε of soft white polyethylene was isolated, the 1 H NMR spectrum of this product shows branched polyethylene peaks at 1.25 ppm (CH 2 ) and 0.85 pp (CH 3 ) Example 122 Ph Ph ~~ 1 + >— < M p e h' N Nr N: Me BAF Tne general εyntheεis of nickel allyl initiators waε followed using 95 mg of ligand, 34 mg of [ (C 3 Hs)Nι (μ-Cl)] 2 , and 218 mg of NaBAF A yellow powder (231 mg) was isolated The 1 H NMR spectrum lε complex with more than one isomer apparently present Example 123 The allyl initiator of Example 122 was used to polymerize ethylene in CDCI3 at 60°C according to the general polymerization procedure using 22 mg of catalyst. A few mg's of polyethylene waε isolated, the 1 H NMP spectrum of this product shows a -(CH2)- peak at 1 2 pp--- The 1 H NMR spectrum of the reaction mixture shows the production of buteneε; branched polyethylene peakε are also observable at 1.25 ppm (CH 2 ) and 0.85 ppm (CH3) Example 124 Ar = 2,4,6-C 6 H 2 -(OMe) 3 The general synthesis of nickel allyl initiators was followed using 213 mg of ligand, 54 mg of [ (C 3 Hs)Nι(μ-Cl)]2, and 354 mg of NaBAF. An orange powder (391 mg) was isolated. Variable-temperature -*-H NMR and 13 C NMR spectra are consistent with the above structure which one methoxy group and the phosphorus atom are coordinated to nickel. ---H NMR spectral data are reported at both -100°C and 20°C. Four resonances for the allyl εyn and anti protons are observed at -100°C, while two resonances are observed at RT for these protons . The observation of the four syn and anti protons at -100°C supports probable coordination of the methoxy group to nickel: -4* NMR (CD2CI2, 300 MHz, -100°C) d 6.05 (d, 6, JHP = 4.1, C w ) , 5.59 (m, 1, H2CCHCH2) , 3.89 (d, 1, J = 6.75, HH'CHCHH'), 3.76 (s, p-OMe), 3.67 (ε, o- OMe) , 3.07 (br s, 1, HH'CHCHH'), 2.93 (dd, 1, J = 13.5, 5.4, HH'CHCHH'), 1.74 (d, 1, J = 12.1, HH'CCHCHH'); -*-H NMR ( D CI2, 300 MHz, 20°C) d 6.13 (d, 6, J H p = 2.7, C m ) , 5.62 (m, 1, H 2 CCHCH 2 ), 3.81 (ε, p-OMe), 3.71 (s, o-OMe) , 3.49 (d, 2, J = 6.8, HH'CHCHH'), 2.42 (d, 2, J = 16.2, HH'CHCHH'); 13 C NMR (CD 2 C1 2 , 75 MHz, rt) d 164.0 (Cp) , 162.4 (d, J C p = 4.9, C 0 ) , 113.7 (H 2 CCHCH 2 ), 97.8 (d, JCP = 60.4, C p S o to P) , 91.1 (d, J = 4.9, C m ) , 57.8 (H 2 CCHCH 2 and o-O e, overlapping), 55.4 (p-OMe) . Example 125 The allyl initiator of Example 124 was used to polymerize ethylene in CDC1 3 at RT according to the general polymerization procedure using 28 mg of catalyst. Butenes were formed according to 1 H NMR spectroscopy. Example 26 The allyl initiator of Example 124 waε used to polymerize ethylene in CζOζ at RT according to the general polymerization procedure using 28 mg of catalyst. Butenes and some higher olefinε were formed according to 1 H NMR spectroscopy. Example 27 Ar = 2,4,6-C 6 H2-(OMe) 3 The general synthesis of nickel allyl initiators waε followed using 501 mg of ligand, 224 mg of [(H 2 C(C0 2 Me)CH 2 )Ni (μ- Br)]2, and 834 mg of NaBAF. A yellow-green powder (391 mg) was isolated. 1 H NMR spectrum of product is complex,- the structure shown above is tentatively assigned by analogy to the parent (C3H5) allyl complex. Example 126 The allyl initiator of Example 127 was used to polymerize 5 ethylene CgDς at RT according to the general polymerization procedure using 93 mg (0.06 mmol) of catalyεt and 2 equiv (29 mg) of BPh 3 cocatalyεt. Polyethylene (177 mg) was isolated. Example 129 The allyl initiator of Example 127 was used to polymerize 10 ethylene in CDCI3 at RT according to the general polymerization procedure using 93 mg (0.06 mmol) of catalyst and 2 equiv (61 mg) of B(Cg ) 3 cocatalyst. Polyethylene (90 mg) waε isolated. Example 130 15 The general synthesis of nickel allyl initiators waε followed using 45 mg of ligand, 50 mg of [ (C 3 Hs)Ni(μ-Cl) ] 2 , and 328 mg of NaBAF. A yellow powder (334 mg) was isolated. The 1 H NMR spectral data is consistent with the structure shown above: • • H NMP (CD 2 C1 , 300 MHz, rt) d 8.46 (d, 1, J = 5.4, H ary ι) , 8.17 20 (t, 1, J = 8.1, Haryl) - -8 (d, 1, J = 8.1, H ary ι), 7.74 (m, 1, Haryl * overlaps with BAF: H σ ) , 7.10 and 6.82 (br s, 1 each NHH'), 5.9S (m, 1, H 2 CCHCH 2 ) , 3.57 (d, 2, J = 6.8, HH'CCHCHH'), 2.66 (d, 2, J = 13.5, HH'CCHCHH') . 13 C NMR (CD 2 C1 2 , 75 MHz, rt) d 173.5 (C=0) , 146.4 (Caryl: C-C(0)NH 2 ), 153.7, 141.4, 131.6 and 123.9 -• ( c aryl attached to hydrogen), 117.2 (H2CCHCH2), (H2CCHCH2 overlaps with CD 2 I resonance) . Example 131 The allyl initiator of Example 130 was used to polymerize ethylene in CDCl 3 at RT according to the general polymerization procedure using 63 mg of catalyst. A few mg's of polyethylene waε isolated. According to the 1 H NMR spectrum of the reaction mixture, significant amounts of butenes and higher olef s were produced. Polyethylene -CH2- resonance is identifiable at 1.25 ppm. Example 132 The allyl initiator of Example 130 was used to polymerize ethylene in C ζ Oζ at 80°C according to the general polymerization procedure using 64 mg of catalyst. Polyethylene (247 mg) waε isolated. According to the 1 H NMR spectrum of the reaction mixture, the reaction was productive in the formation of butenes and higher olefms. Example 133 The general synthesiε of nickel allyl initiators was followed using 52 mg of ligand, 50 mg of [ (C 3 Hs)Nι (μ-Cl) ]2, and 328 mg of NaBAF. A yellow powder (328 mg) was isolated. The 1 H NMR spectral data is consistent with the structure shown above: 1 H NMP (CD2CI2, 300 MHz, rt) d 11.34 (br s, 1, OH), 8.54 (br s, 1, NHH'ϊ, 7.99 (d, 1, J = 4.0, H ary ι) , 7.64 (d, 1, J = 8.1, H ary ι) , 7.55 (t, 1, J = 4.7, H ary i), 6.76 (br ε, 1, NHH'), 5.95 (m, 1, HH'CCHCHH'), 3.40 (br, HH'CCHCHH', 2.58 (br, HH'CCHCHH'). 13 C NMR (CD2CI2, 75 MHz, rt, assignments aided by an APT spectrum) δ 173.7 (CO), 155.9 and 133.8 (C ar yl not attached to hydrogen), 145.8, 132.3 and 129.3 (C ary l attached to hydrogen), 116.6 (H2CCHCH2) , (H2CCHCH 2 resonances not observed Neither overlapping with CD2CI resonance or broad and in the baseline) . Example 134 The allyl initiator of Example 133 waε used to polymerize ethylene in CDCl 3 at RT according to the general polymerization procedure using 60 mg of catalyst. Polyethylene (190 mg) was isolated as a white powder. Example 135 The allyl initiator of Example 133 was used to polymerize ethylene CζDζ at 80°C according to the general polymerization procedure using 60 mg of catalyst. Polyethylene (783 mg) was isolated According to the NMR spectrum of the reaction mixture, significant amounts of butenes and higher olefms were produced Example . 36 The general εynthesiε of nickel allyl initiators waε followed using 57 mg of ligand, 50 mg of [ (C 3 Hs)Nι (μ-Cl) ] 2, and 328 mg of NaBAF A yellow powder (264 mg) was lεolated. The 1 H, 1_ C, and APT NMR spectral data is consistent with the structure snown above 1 H NMR (CD2CI 2 , 300 MHz, rt) d 14.0 (br ε, 1, OH) , 8.10 (d, 1, J = 8.1, H ary l), 7.65 (t, 1, J = 8.1, H ary l), 7.47 (t, 1, J = 8 1, H ary ι) , 7.21 (d, 1, J = 8.1, H ar yl), 5.83 (m, 1, H2CCHCK2) , 4.34 (br ε, 2, NH 2 ) , 3.23 (br d, 2, J = 5.4, HH'CCHCHH'), 2.34 (br d, 2, J = 13.49, HH'CCHCHH') Example 137 The allyl initiator of Example 136 was used to polymerize ethylene in CDC1 3 at RT according to the general polymerization procedure using 63 mg of catalyst. Polyethylene was not isolated. According to the 1 H NMR spectrum of the reaction mixture, significant amounts of butenes and higher olefms were produced. Example 136 The general synthesis of nickel allyl initiators was followed using 83 mg of ligand, 50 mg of [ (C 3 Hs)Ni(μ-Cl)]2, and 328 mg of NaBAF. A red powder (381 mg) was isolated. 1 H NMR (CD2Cl 2 , 300 MHz, rt) : The complex formed a clear red solution in CD 2 C1 2 with no precipitate present. However, the lock signal and spectrum were both broad, possibly indicating paramagnetiεm. The above structure is tentatively assigned by analogy to diamagnetic complexes containing ligandε with similar donor functionality. Example 139 The allyl initiator of Example 138 was used to polymerize ethylene CDC1 3 at RT according to the general polymerization procedure using 63 mg of catalyεt. Polyethylene (88 mg) waε lεolated. Example 140 The allyl initiator of Example 138 was used to polymerize ethylene in CςDg at 80°C according to the general polymerization procedure using 60 mg of catalyst. Polyethylene (64 mg) was isolated. According to the 1 H NMR spectrum of the reaction mixture, significant amounts of butenes and higher olefms were produced. Example 141 Tne general syntheεiε of nickel allyl itiatorε waε followed using 135 mg of ligand, 50 mg of [ (C 3 Hs)Nι(μ-Cl) ]2, and 328 mg of NaBAF. An orange powder (403 mg) waε isolated. The " " " H, 13 C, and APT NMR spectral data for the major product follows and is conεiεtent with one lεomer of the above εtructure. Other isomerε may be present in lesser amounts: 1 H NMR (CD2CI2, 300 MHz, rt) d 9.77 and 8.83 (s, 1 each, N=CH and H ar yl) , 9.0 - 7.5 (m, 6, K ar yl), 6.91 and 6.63 (br ε, 1 each, NHH'), 4.6 (br ε, 1, H 2 CHCH 2 ) , 3.5 - 2.3 (broad resonanceε in the baseline, HH'CCHCHH') . 13 C NMR (CD2CI2, 75 MHz, rt, assignments aided by an APT spectrum) d 173.7 (N=CH) , 172.9 (CO), 147.4, 131.6, 131.0, 126.5 and 124.7 (C a ryl no attached to hydrogen), 136.8, 133.7, 130.3, 130.2, 129.5, 129.3, 127.0, 123.3 and 122.7 (C ary l attached to hydrogen), 113.8 (H2CCHCH2) , (H 2 CCHCH 2 resonances were not observedNeither overlapping with CD2CI2 resonance or broad and in the baseline) . Example 142 The allyl initiator of Example 141 was used to polymerize ethylene in CDC1 3 at RT according to the general polymerization procedure using 68 mg of catalyεt. Polyethylene (1.60 g) waε lεolated as a wax. Example 143 The allyl initiator of Example 141 was used to polymerize ethylene in CgDβ at 80°C according to the general polymerization procedure using 60 mg of catalyst. Polyethylene (5.64 g) was isolated aε a wax. Example 144 The general synthesis of nickel allyl initiators waε followed using 123 mg of ligand, 50 mg of [ (C H5>Nι (μ-Cl) ] 2, and 328 mg of NaBAF. A yellow powder (383 mg) was isolated. The 1 K NMR spectrum is conεiεtent with the above structure, although contamination by free ligand is indicated: **-H NMR (CD2CI2, 300 MHz, rt, i-Pr and allyl resonances only) d 5.97 (tn, 1, H2CCHCH2) , 3.76 (br septet and br d, 1 each, CHMe 2 and HH'CHCHH'), 3.53 (br d, 1, J - 5.5, HH'CCHCHH'), 3.35 (br septet, 1, CHMe 2 ), 2.53 (br d, 1, J = 13.6, HH'CCHCHH'), 2.20 (br d, 1, J = 13.6, HH'CCHCHH'), 1.45, 1.43, 1.29 and 1.15 (d, 3 each, J = 6.6 - 7.7, CHMeMε' and C'HMeMe' ) Example 145 The allyl initiator of Example waε 144 uεed to polymerize ethylene in CDCI3 at RT according to the general polymerization procedure using 40 mg of catalyst. Polyethylene (30 mg) was isolated as a white powder. According to the 1 H NMR spectrum of the reaction mixture, significant amounts of buteneε and higher olefms were produced. Minor resonances consistent with the formation of branched polyethylene are present. Example 146 The allyl initiator of Example 144 was used to polymerize ethylene C6U6 at 80°C according to the general polymerization procedure using 64 mg of catalyεt. Polyethylene (96 mg) waε lεolated as a white powder. The 1 H NMR spectrum shows the production of butenes and higher olefinε. Polyethylene -CH2- resonance s identifiable at 1.25 ppm. Example 147 The general εynthesis of nickel allyl initiators waε followed using 532 mg of ligand, 229 mg of [ (C 3 Hs) i(μ-Cl) ] 2 , and 1.50 of NaBAF. 1.85 g of a yellow powder waε iεolated. Although the free ligand exiεts as the amme, the 1 H and 13 C NMR spectra are consistent with the ligand binding to the molecule as the imme- -"-H NMR (THF-dg, 300 MHz, rt) d 8.75 (br ε, 2, NH 2 ) , 8.55 (d, 1, J = 5.4, N=CH) , 7.9 - 7.0 (m, 14, H ar yl), 5.56 (d, 1, J = 5.4, CHPh ) , 5.52 (m, 1, H 2 CCHCH 2 ), 3.01 (d, 2, J = 6.7, HH'CCHCHH'), 2.01 (d, 2, J = 13.5, HH'CCHCHH'); 13 C NMR (THF-dg, 75 MHz, rt, non-aromatic carbons only, assignments aided by APT spectrum) d 181.7 (N=CH) , 172.8 (C=0) , 113.8 (H 2 CCHCH2) , 58.7 (CHPh 2 ), 54.5 (H 2 CCHCH 2 ) . Example 148 The allyl initiator of Example 147 was used to polymerize ethylene n CDC1 3 at RT according to the general polymerization procedure using 40 mg of catalyεt. Polyethylene (25 mg) waε lεolated aε a white powder. According to the 1 H NMR spectrum of the reaction mixture, butenes were formed along with higher olefms; the major product is consistent with branched polyethylene [1.25 (CH2) , 0.85 (CH 3 )] with approximately 100 methyl-ended branches per 1000 carbon atoms. Example 149 The allyl initiator of Example 147 was used to polymerize ethylene in CζΩe at RT according to the general polymerization procedure using 75 mg of catalyst. Polyethylene (588 mg) was isolated as a white powder. Example 150 The allyl initiator of Example 147 waε used to polymerize ethylene CζOζ at 80°C according to the general polymerization procedure using 61 mg of catalyst. Polyethylene (1.39 g) was isolated. According to the 1 H NMR spectrum of the reaction mixture, significant amounts of butenes and higher olefms were produced A significant polyethylene -CH2- peak appears at 1.25 ppm. Example 151 The general synthesis of nickel allyl initiators waε followed uεing 255 mg of ligand, 105 mg of [ (C 3 Hs)Ni(μ-Cl) ] 2 , and 685 mg of NaBAF. 772 mg of a pale green powder was isolated. Example 152 The allyl initiator of Example 151 was used to polymerize ethylene CDC1 3 at RT according to the general polymerization procedure using 45 mg of catalyεt Polyethylene (1.61 g) waε lεolated aε a white powder Example 153 The allyl initiator of Example 151 waε used to polymerize ethylene m CζΩζ at RT according to the general polymerization procedure using 62 mg of catalyst Polyethylene (93 mg) was isolated aε a white powder. The 1 H NMR spectrum εhowε the production of buteneε and higher olef s Polyethylene -CH2- resonance is identifiable at 1.25 ppm Example 154 The allyl initiator of Example 151 was used to polymerize ethylene m C&Ωs at 80°C according to the general polymerization procedure using 67 mg of catalyεt Polyethylene (169 mg) was lεolateo According to the 1 H NMR spectrum of the reaction mixture the reaction was productive in the formation of buteneε and higher olefms Polyethylene -CH2- resonance is identifiable at 1 25 ppr Example 155 CO 2 Me The general syntheεiε of nickel allyl initiators was followed using 213 mg of ligand, 295 mg of [ (H2CC(C0 2 Me)CH2) ι(μ- Br)] 2 , and 795 mg of NaBAF A gold powder (0.792 g) was isolated Example 156 The allyl initiator of Example 155 was used to polymerize ethylene C ζ Oς, at RT according to the general polymerization procedure using 61 mg of catalyst. Polyethylene (1.97 g) waε isolated aε a white powder. Example .157 The general synthesiε of nickel allyl mitiatorε waε followed using 657 mg of ligand, 238 mg of [ (H 2 CCHCMe2)Ni (μ-Br) ] , and 1.56 of NaBAF. A red powder (1.88 g) was isolated. Although the free ligand exists aε the amme, the 1 H and 13 C NMR spectra are conεiεtent with the ligand binding to the molecule aε the imme: 1 H NMP (CD2CI2, 300 MHz, rt) d 8.41 (d, 1, J = 5.4, N=CH) , 7.8 - 6.8 ( , 17, H a ryl), 5.42 (d, 1, J = 5.4, CHPh 2 ), 4.80 (dd, 1, J = 12.8, 6.9, H 2 CCHCMe2), 2.95 (d, 1, J = 6.7, HH'CCHCMe 2 ), 2.03 (d, 1, J = 13.5, HH'CCHCMe 2 ) , 0.77 (s, 6, H 2 CCHCMeMe') ; 13 C NMR (CD 2 CI 2 , 75 MHz, rt, non-aromatic carbons only, assignments aided by AFT spectrum) d 202.4 (C=θ), 182.6 (N=CH) , 109.1 (H 2 CCHCMe 2 ) , 59.7 (CHPh 2 ), 53.2 (H 2 CCHCMe 2 ), 43.1 (H 2 CCHCMe ), 26.0 and 20.8 (H 2 CCHCMeMe') . Example 158 The allyl initiator of Example 157 waε uεed to polymerize ethylene in CζΩζ at RT according to the general polymerization procedure using 61 mg of catalyst. According to the - 1 -H NMR spectrum, significant amounts of butenes and higher olefinε were produced. Example 159 The allyl initiator of Example 157 waε used to polymerize ethylene in CζOζ at 80°C according to the general polymerization procedure using 63 mg of catalyst. According to the 1 H NMR spectrum of the reaction mixture, significant amounts of butenes and higher olefins were produced For Exampleε 160 - 177 where the ligandε are thiophene and furan derivativeε, the 1 H NMR spectra of the productε are, in general, complex and include more than one species. The structural asεignmentε of theεe complexeε are therefore tentative. Example J.6Q The general synthesis of nickel allyl initiators was followed using 115 mg of ligand, 50 mg of [ (C 3 Hs)Nι (μ-Cl) ] 2, and 328 mg of NaBAF. A sticky dark-red solid (185 mg) was isolated. Example 161 The allyl initiator of Example 160 was used to polymerize ethylene CDC1 3 at RT according to the general polymerization procedure (with the exception that 5.2 MPa of ethylene was used) using 57 mg of catalyst. Polyethylene waε not isolated. According to the 1 H NMR εpectrum of the reaction mixture, εignificant amountε of buteneε and higher olefms were produced. Example 162 The general εyntheεiε of nickel allyl initiatorε waε followed using 173 mg of ligand, 87 mg of [ (C 3 Hs)Ni (μ-Cl) ] 2 , and 570 mg of NaBAF. An orange powder (705 mg) was isolated. Example 163 The allyl initiator of Example 162 was used to polymerize ethylene in CDC1 3 at RT according to the general polymerization procedure using 64 mg of catalyst Polyethylene (72 mg) waε isolated The 1 H NMR spectrum of the reaction mixture indicates that significant amounts of buteneε and higher olefms were produced Example 164 The allyl initiator of Example 162 was used to polymerize ethylene m CζOβ at 80°C according to the general polymerization procedure using 68 mg of catalyst. Polyethylene (77 mg) waε lεolated The 1 H NMR spectrum of the reaction mixture indicates that significant amountε of buteneε and higher olefms were produced Example 165 Tne general εyntheεiε of nickel allyl initiators was followed using 65 mg of ligand, 50 mg of [ (H 2 CCHCMe )Nι (μ-Br) ] 2 , and 213 mg of NaBAF An orange powder (163 mg) waε lεolated Example 166 The allyl initiator of Example 165 was uεed to polymerize ethylene CDCI3 at RT according to the general polymerization procedure using 40 mg of catalyεt. Polyethylene (823 mg) was iεolated as a white powder. Example 167 The allyl initiator of Example 165 waε used to polymerize ethylene C β Dg at 80°C according to the general polymerization procedure using 63 mg of catalyεt. Polyethylene waε not isolated, however, the 1 H NMR spectrum of the reaction mixture indicates that significant amounts of butenes and higher olefins were formed. Example 168 The general εynthesiε of nickel allyl initiators was followed using 311 mg of ligand, 274 mg of [ (H2 C(Cθ2 e)CH2>Ni (μ- Br)] , and 1.02 g of NaBAF. An orange powder (1.30 g) waε isolated. Example 169 The allyl initiator of Example 168 was uεed to polymerize ethylene in CDC1 3 at 80°C according to the general polymerization procedure using 77 mg of catalyεt and 1 equiv (31 mg) of B(CgF5) 3 cocatalyεt. Polyethylene (188 mg) was isolated as a waxy solid. The 1 H NMR spectrum of the reaction mixture indicates that significant amounts of buteneε and higher olefins were produced; the polyethylene -CH 2 - resonance is identifiable at 1.25 ppm. Example 170 The general syntheεiε of nickel allyl initiatorε waε followed using 323 mg of ligand, 153 mg of [ (C 3 Hs)Ni (μ-Cl) ] 2 , and 1.00 g of NaBAF. An orange powder (1.22 g) was iεolated. Example 171 The general syntheεiε of nickel allyl initiatorε waε followed using 329 mg of ligand, 239 mg of [ (H 2 CCHCMe2>Ni(μ-Br) ] 2 , and 1.02 mg of NaBAF. A εticky red solid (742 mg) was isolated. Example 172 The allyl initiator of Example 171 waε used to polymerize ethylene n CςDβ at RT according to the general polymerization procedure using 77 mg of catalyst. Polyethylene (100 mg) was lεolated. The 1 H NMR spectrum of the reaction mixture indicates that significant amounts of butenes and higher olefms were produced. Example 173 The general syntheεis of nickel allyl initiatorε waε followed using 327 mg of ligand, 272 mg of [ (C 3 Hs)Nι (μ-Cl)]2, and 1.01 g of NaBAF. An orange powder (1.42 g) waε isolated. Example 174 Tne allyl initiator of Example 173 waε uεed to polymerize ethylene in ςOζ at RT according to the general polymerization procedure uεmg 78 mg of catalyst and 2 equiv (29 mg) of BPh 3 cocatalyεt . Polyethylene was not isolated. The i H NMR spectrum of the reaction mixture indicates that significant amounts of butenes and higher olefms were produced. Example 175 The allyl initiator of Example 173 waε uεed to polymerize ethylene CDC1 at 80°C according to the general polymerization procedure using 78 mg of catalyεt and 1 equiv (31 mg) of B(CgF5) 3 cocatalyεt. Polyethylene (2.39 g) waε isolated. Example 7 The above general procedure for nickel allyl initiators was followed using 62 mg of ligand, 50 mg of [ (H CCHCMe2)Ni (μ-Br) ] 2, and 213 mg of NaBAF. An orange powder (188 mg) waε isolated. Example 77 The allyl initiator of Example 176 was used to polymerize ethylene n CDC1 3 at RT according to the general polymerization procedure using 40 mg of catalyεt. No polyethylene waε isolated Example 178 Ar = 2,6-C 6 H3- -Pr 2 The general synthesis of nickel allyl initiators was followed using 462 mg of ligand, 153 mg of [ (C 3 Hs)Nι (μ-Cl)] 2 , and 1.00 g of NaBAF. A beige powder (1.68 g) was isolated The stability of the complex is poor in CD2CI2 and THF-dg at RT Only broad NMR εpectra were obtained The above structure is therefore tentatively aεs gned Example 179 The allyl initiator of Example 178 was used to polymerize ethylene in CζOζ at RT according to the general polymerization procedure using 82 mg of catalyst. Polyethylene waε not lεolated. Example 18Q The allyl initiator of Example 178 was used to polymerize ethylene m CDC1 3 at 80°C according to the general polymerization procedure using 82 mg of catalyst Polyethylene (2.01 g) waε isolated Example 181 Ar = 2,6-C6H 3 -Me 2 The general synthesis of nickel allyl initiators waε followed using 462 mg of ligand, 211 mg of [ (C 3 H5)Nι (μ-Cl) ] 2, and 1 36 mg of NaBAF. A pale orange powder (2.16 g) was isolated. The stability of the complex is poor in CD2 C1 2 and THF-dg at RT. Only broad NMR spectra were obtained. The above structure is therefore tentatively assigned. Example 182 The allyl initiator of Example 181 waε used to polymerize ethylene in CgDg at RT according to the general polymerization procedure using 76 mg of catalyst. Polyethylene (147 mg) waε lεolated Example 163 The allyl initiator of Example 181 waε used to polymerize ethylene in CDC1 3 at 80°C according to the general polymerization procedure using 76 mg of catalyst. Polyethylene (434 mg) was isolated Examples 184 - 177 Following the procedure of Examples 23 - 66, ethylene was polymerized The results are reported in Table 6. The structures of the ligands are listed after Table 6. Table 6 Example 168 Synthesis of 50 9-Anthraldehyde (3.70 g) was dissolved in 100 ml THF in a 200 ml round bottom flask. To the hot solution waε added dropwise 2.77g 2-anthranilamide (in 20 ml THF) . Then 4 drops of formic acid were added to the mixture. Soon after adding the formic acid, yellow precipitate began to form. Heating and stirring were continued for another 2 h. After cooling, the solid was isolated by filtering, followed by waεhing with methanol and THF to remove excess 2-anthranilamide. TLC (5:1 hexane:ethyl acetate) showed a single new band. The dried product weighed 3.5g. 1 H NMR (DMSO, δ ppm! :9.82 (s, lH) ;8.90(m, 3H) ;8.25(m, 3H);7.90(d, 1) ;7.67.7 (m, 7H! ;7.45 (t, 1) . Example .189 Synthesis of 66 1, 1-Dιphenylacetaldehyde (0.4906 g) waε diεεolved in 30 ml methanol. To this hot solution was added 0.4881 g l-amιno-9-fluorenone (m methanol) . Then 6 drops of formic acid was added to catalyze the reaction. Soon after adding the formic acid, the color of the solution changed from yellow to orange red, then to deep red. At this point, TLC (3:1 hexane:ethyl acetate) showed the appearance of new bands. When cooled, a red precipitate formed. The precipitate was isolated by filtering followed by washing with methanol and hexane. The dried product weighed 0.4g. The 1 H, 13 C and APT spectra are consistent with the existence of the product as the enamine structure shown above. In addition the structure was confirmed by X-ray crystallography. -*-H NMR (CD 2 C1 2 , 300 MHz, rt) d 9.25 (d, 1, J = 12.1, NH) , 7.6 - 6.85 ( , 18, H ary l and CH=CPh 2 ) ; 13 C NMR (CD 2 C1 , 75 MHz, rt, aεεign entε were aided by an APT spectrum) d 194.0 (C=0) , 144.6, 143.1, 142 7, 141.2, 137.7, 134.7 121.3 and 115.15 (C ary ι not attached to hydrogen and =C h2) , 136.6, 133.6, 130.1, 129.2, 128.9, 128.3, 127.6, 126.5, 126.1, 123.1, 121.9, 120.4, 112.7 and 110.8 (Caryl attached to hydrogen and =CHNHAr) . Example 190 Synthesis of. 63 l-Ammoanthraqumone (2.2323 g) waε dissolved in a 1:1 mixture of methanol and THF. To the hot solution was added 1 .9625g 1, 1-dιphenylacetaldehyde. Then 8 drops of formic acid was added as catalyst After refluxmg for 4 h, heating was removed. TLC (5 1 hexane:ethyl acetate) showed the appearance of a new band which was purple The solvent was removed by rotary evaporator. The solid waε resuspended in ether and stirred. Filtered to collect the solid, followed by washing with a large amount of ether until a single band was obtained. Pure product waε also obtained by silica gel chromatography to give a purple solid. Yield 1.2g X H NMR (CD 2 C1 2 , δ in ppm) :11.75 (d, lH);8.20(m, 2H) ,7.25-7.85 (m, 16H) . Example 131 Synthesis of 54 1, 1-Dιphenylacetaldehyde (3.9250 g) waε d εεolved in 30 ml anhydrous methanol To thiε refluxmg εolution waε added 2.7230 g 2-anthranιlamιde (in methanol) . Soon a yellow precipitate formed. After all the 2-anthranιlamιde was added, heating and stirring were continued for another hour. When cooled, the solid was isolated cy filtering. The solid waε then reεuspended in methanol, stirred and then filtered Yield 5.lg. The 1 K, 13 C, and APT spectra are consiεtent with the exiεtence of the product aε the enamme structure shown above: ^ H NMR (THF-dg, 300 MHz, rt, aεεignmentε were aided by an APT spectrum) δ 10.86 (br d, 1, J = 12.10, NH-CH=CPh 2 ) , 7.60 - 6.85 (m, 16, H ar yl, CH=CPh , C(O)NHH'), 6.60 (br ε, 1, C(O)NHH'); 13 C NMR (THF-dg, 75 MHz, rt, aεεignments were aided by an APT spectrum) δ 171.9 (C=0) , 145.9, 143.4, 139.7, 120.0 and 116.6 (C ar yl not attached to hydrogen and =CPh 2 ), 113.4, 131.1, 129.4, 128.8, 127.4, 125.9, 124.9, 117.8 and 113.4 (Caryl attached to hydrogen and =CHNAr) . Example 192 Synthesis of 56 1, 1-Diphenylacetaldehyde (4.0138 g) was dissolved in 20 ml anhydrous methanol. To thiε hot solution was added 3.0918 g methyl anthranilate (in methanol) . The color of the solution changed from colorlesε to yellow as soon as two components were mixed. After adding all the methyl anthranilate, the heat waε turned off. During cooling, a yellow precipitate began to form. The precipitate waε collected by filtering followed by washing with methanol. After recrystallization in methanol, 2.6g product was obtained. The 1 H, 13 C, and APT spectra are consistent with the existence of the product as the ena ine structure shown above. In addition, thiε structure waε confirmed by X-ray crystallography. 1 H NMR (CD 2 C1 2 , 300 MHz, rt) δ 9.94 (br d, 1, J = 11.73, NH) , 8.05 - 6.75 ( , 15, H ary l and =CHNHAr) , 3.78 (s, 3, OMe) ; 13 C NMR (CD 2 C1 , 75 MHz, rt, asεignmentε were aided by an APT spectrum) δ 168.0 (C=0) , 145.4, 141.9, 138.4, 120.9 and 112.1 (C ar yl not attached to hydrogen and CH=CPh 2 ) , 134.6, 132.0, 130.3, 129.0, 128.4, 127.3, 126.7, 125.9, 123.4, 117.7 and 112.4 (C ary ι attached to hydrogen and CH=CPh2) , 51.8 (OΛfe) . Example 193 Synthesis of 58 9-Anthraldehyde (2.0624 g) was dissolved in 60 ml of a 1:1 mixture of methanol and THF (the 9-anthralaldehyde did not dissolve completely in methanol) . To this refluxmg solution waε added dropwiεe 1.7729g 2,6-diιεopropylanilme. When the addition waε complete, 4 dropε of formic acid were added as catalyst. The solution was refluxed for another 2 h before it was cooled. After standing overnight, a yellow solid precipitated. The solid was isolated by filtering followed by washing with methanol. Yield 2.5g of dried product. X H NMR (CD 2 C1 2 , δ in ppm) : 9.51(s, lH);9.05(d, 2H);9.20(ε, lH);8.20(d, 2H);7.65(m, 4H);7.30(d, 2H);7.25(t, 1H) ,-3.30(hep, 2H);1.30(d, 12H) . Example 194 05 + NaBAF Tne general εyntheεiε of nickel allyl initiators waε followed using 136 mg of ligand, 53 mg of [ (C Hs)Nι(μ-Cl) ] , and 342 mg of NaBAF. A yellow powder (430 mg) was isolated. Example 195 ■ The allyl initiator of Example 194 waε uεed to polymerize ethylene C ζ Oβ at 80°C according to the general polymerization procedure uεmg 64 mg of catalyεt. Polyethylene (104 mg) was isolated. The 1 H NMR spectrum of the reaction mixture showed that significant amounts of buteneε and higher olefinε were produced. Example 196 05 ((-N ' .Nr- + + NaBAF The general εyntheεis of nickel allyl initiators waε followed using 129 mg of ligand, 51 mg of [ (C 3 Hs)Nι(μ-Cl) ] 2 , and 317 mg of NaBAF. A sticky orange solid (217 mg) was isolated. Example 197 The allyl initiator of Example 196 was used to polymerize ethylene n CDC1 3 at 60°C according to the general polymerization procedure using 24 mg of catalyεt. The ethylene preεsure waε initially 1.2 MPa and waε increased to 6.9 MPa after l h. A few mg's of polyethylene was produced. The 1 H NMR spectrum of the reaction mixture showed that significant amounts of butenes and higher olefms were produced. Example 198 05 <(-N. ' + NaBAF The general syntheεiε of nickel allyl initiatorε waε followed using 136 mg of ligand, 49 mg of [ (C 3 Hs)Nι(μ-Cl) ]2, and 309 mg of NaBAF. An orange powder (380 mg) was isolated. Example i?9 The allyl initiator of Example 198 was used to polymerize ethylene in CβDg at RT at 5.2 MPa according to the general polymerization procedure using 63 mg of catalyεt. Polyethylene (29 mg) was isolated. The 1 H NMR spectrum of the reaction mixture showed that significant amounts of butenes and higher olefms were produced Example 200 05 {{— + NaBAF The general synthesis of nickel allyl initiators was followed using 111 mg of ligand, 50 mg of [ (C 3 Hs)Ni (μ-Cl)]2, and 328 mg of NaBAF. An orange powder (347 mg) waε isolated. Example,.202 The allyl initiator of Example 201 was used to polymerize ethylene in CDCl 3 at 60°C according to the general polymerization procedure using 23 mg of catalyst. The ethylene presεure waε initially 1.4 MPa and waε increased to 6.9 MPa after 1 h. A few mg'ε of polyethylene waε produced. The 1 H NMR spectrum of the reaction mixture showed that significant amounts of butenes and higher olefms were produced. Example 203 Using 5 47 g of 1,1-dιphenylacetaldehyde and 3.60 g of 2,6- dimethylamlme, 5 79 g of an orange powder waε obtained following a εyntheεis analogous to that of the 2,6-dιιεopropylanιlme derivative given above The -*-H, 13 C, and APT εpectra are conεistent w th the exiεtence of the product aε the enam e εtructure εhown above: -*-H NMR (CDC1 3 , 300 MHz, rt) δ 7.6 - 7.0 (m, 13, Haryl)- 6 - 88 < d - -*•• J = 12-1, ArNHCH-=CPh2 ) , 5.47 ( d, 1, J = 12.1, ArNHCH=CPh ) , 2.37 (ε, 6, C6H 3 -Me 2 ) ; 13 C NMR (CDC1 3 , 75 MHz, rt, aεεignments aided by an APT spectrum) δ 142.0, 140.7, 13e.9 and 131.1 (Ph: Cι pso ; Ph' : Cιp SO ; Ar: Cι pso and C 0 ) , 131.6, 130.6, 129.3, 128.9, 128.3, 126.9, 125.4, 124.8 and 123.8 (Ph: C 0 , C IΓ , Cp; Ph' • C 0 , C m , C p ; Ar: C m , C p ; CH=CPh ), 114.0 (CH=CPh 2 ), 13.8 (CgH 3 -ftfe2) • Example 204 Using 5.43 g of 1,1-dιphenylacetaldehyde and 2.71 g of aniline, 5.68 g of yellow powder was obtained following a syntheεiε analogouε to that of the 2,6-diisopropylanilme derivative given above. The 1 H, 13 C, and APT spectra are consiεtent with the existence of the product as the enamine structure shown above: 1 H NMR (CDC1 3 , 300 MHz, rt) δ 7.6 - 6.8 (m, 15, H ary l), 7.18 (d, 1, J = 12.1, PhNHCH=CPh2) , 6.12 (d, 1, J = 11.8, PhNHCH=CPh 2 ) ; 13 C NMR (CDC1 3 , 75 MHz, rt, assignmentε were aided by an APT spectrum) δ 142.7, 141.8 and 138.5 (Ph: Ci pso ; Ph' : Cipso; Ph 1 ' : Ci pS o), 130.5, 129.6, 129.3, 128.4, 127.2, 126.2, 125.5, 124.8, 120.0 and 113.9 (Ph: C c , C m , C p ; Ph': C, Cp; Ph' ' : C 0 , C m , C p ; CH=CPh 2 ) , 117.7 (CH=CPh 2 ) . Example 205 solution of 1.02 g of 2,3-butanedione in 10 mL of MeOH and 2.92 g of 2-amino-m-cresol were mixed together in a round bottom flask. Formic acid (10 drops) was added via pipette. After -1.5 h, a precipitate had formed. The solution was stirred overnight and the next day the precipitate was collected on a frit and washed with methanol . The product waε then dissolved in Et 2 0 and stirred overnight over Na 2 S0 4 . The solution was filtered through a frit with Celite and the solvent was removed in vacuo. A light pink powder was obtained (1.72 g) . The and 13 C are conεistent with the product existing aε the cyclized diamine rather than aε the diimine . [Note-. Literature precedent for this cyclization reaction exiεtε, such as in the reaction of o-aminophenol with glyoxal or the reaction of o-aminobenzoic acid with glyoxal. See: Kliegman, J. M. ; Barnes, R. K. J. Org . Chem . 1970, 35 , 3140 - 3143.] : 1 H NMR (CDC1 3 , 300 MHz, rt) δ 6.9 - 6.5 (m, 6, H ar yl) , 4.58 (ε, 2, NH) , 2.20 and 1.62 (ε, 6 each, Me, Me 1 ) ; 13 C NMR (CDCI3, 75 MHz, rt) δ 141.7, 127.1 and 122.3 (Ar: Ci pso , C 0 , C 0 ' ) , 122.6, 119.8, 114.9 (Ar: C m , C m ' , C p ) , 82.0 (-OC(Me)NH-) , 22.1 and 16.7 (Me, Me') . Example 206 n a nitrogen-filled drybox, 20.01 g of lithium 2,6- diisopropylanilide was placed in a 2-neck round bottom flask and dissolved in 300 mL of Et2θ. A 60 mL solution of 6.93 g of oxalyl chloride was placed in an addition funnel. The oxalyl chloride was added to the reaction mixture over a period of several hours and the mixture waε then stirred overnight. Some of the product precipitate out of the Et2θ solution along with the LiCl. Some of the Et θ waε removed in vacuo and enough THF was added to dissolve the product. The solution was filtered through a frit with Celite, the Celite waε washed with THF, and the εolvent waε removed in vacuo. The product waε washed with pentane and pumped dry to give 20.72 g of an off-white powder: - L H NMR (CDC1 3 , 300 MHz, rt) δ 9.26 (br ε, 2, NH) , 7.23 - 7.04 (m, 6, H ary l), 2.94 (septet, 4, CHMe 2 ) , 1-09 (d, 24, CHAfe2 ) . Following the synthetic procedure of the above example, 7.49 g of oxalyl chloride and 15.00 g of lithium 2,6-dιmethylanilιde waε uεed to εynthesize 23.98 g of product, which waε isolated aε an off-white powder: 1 H NMR (CDC1 3 , 300 MHz, rt) δ 9.53 (br 2, 2, NH , 7.0C - 6.86 ( , 6, H a ryl- • 2 * 10 < ε - 12 - Me > • Example 208 Formic acid catalyεt (- 1 mL) waε added to a methanol solution of diphenylacetaldehyde (4.44 mL) and 2,6- dnsopropylaniline (3.18 mL) . After - 15 minutes of stirring, a white precipitate formed. The reaction mixture was stirred for εeveral dayε before the precipitate waε collected on a frit and washed with methanol. The product was then dissolved in Et θ and stirred over Na2S0 4 overnight. The solution was filtered through a frit with Celite and the solvent was removed in vacuo to yield the product. The 1 H, 13 C, and APT spectra are consistent with the existence of the product as the enamine structure shown above: -*-H NMR (CD 2 C1 2 , 300 MHz, rt) δ 7.6 - 7.0 (m, 13, H ary l) , 6.71 (d, 1, J = 12.1, =CHNHAr) , 5.37 (d, 1, J = 12.5, NHAr) , 3.34 (septet, 2, J = 6.9, CHMe 2 ) , 1-25 (d, 12, J = 7.0, CHMe 2 ) ; 13 C NMR (CD 2 C1 2 , 300 MHz, rt, assignments were aided by an APT spectrum) δ 144.9 (Ar C ol , 142. 139.3 and 138.5 (Ar : Cι pso , Ph : Cι pεc Ph' Cipso ) , 133. S. 130.9, 129.' 128.6, 127. 126. 125.4, 124 7 and 124.0 (Ph- C 0 , C m , C p ; Ph' o, m , C p ; Ar: C m , C p , Ph 2 C=CH) , 113.4 (Ph 2 C=CK) , 28.6 (CHMe2) , 23.9 ( CHWe 2 ) . Examples 209-217 Tne wines m the following table were syntheεized using Procedures A and B below Details are shown in the Table. A ..Formic acid catalyst was added to a methanol solution of tne aldehyde and the aniline The reaction mixture waε stirred and the resulting precipitate was collected on a frit and washed wi t h methanol The product was then dissolved in Et2θ or CH Cl 2 and s t irred over Na 2 S0 4 overnight. The solution waε filtered tnrouσn a fr t with Celite and the solvent waε removed in vacuo to yield the product. B. A CH 2 C1 εolution of the aldehyde and the aniline waε s t irred over sodium sulfate Tne solution waε filtered through a fri t with Celite and the solvent was removed in vacuc If necessary, the product was purified by heating in vacuo to remove excess aniline and/or by recrystallization. Example Ligand Synthesis and NMR Data 209 Procedure A. 1 H NMR (CDC1 3 , 30C MHz, rt) δ 8.97 (s, 1, CH=N) , 8.43 (dd, 1, J = 7.8, 1.6, Haryl) , 7.64 (dd, 1, J = 7.6, 1.3, K ary l) , 7.55 (t, 1, J = 7.2, Haryl) , 7.46 (td, 1, J = 7.4, 1.7, H ary l) , 7.37 (ε, 2, Haryl) , I- 37 (s, 9, CMe 3 ) , 1.28 (s, 18, CMe 3 ) , 1.21 (s, 9, CMe 3 ) . 210 Procedure A. 1 H NMR (CDC1 3 , 300 MHz, rt) δ 15.30 (ε, 1, OH), 9.09 (s, 1, N=CH) , 8.1 - 7.2 (m, 9, Haryl ) , 3 *12 ( septet, 2, CHMe 2 ) , 1.25 (d, 12, CHMe 2 ) ; 13 C NMR (CDCI3, 75 MHz, rt) δ 161.7 (C=N) . Example 218 In a dry and oxygen free atmosphere, the allyl initiator of Example 168 (16 mg) was dissolved in dry CH2C1 2 (2 ml) . 5- Ethylidene-2-norbornene (1.8 g) waε added. The orange solution warmed and darkened. After stirring for 17 hours the reaction waε quenched by addition of methanol and the solid polymer filtered, washed well with methanol and dried. Yield = 1.6 g (89%) . 1 H-NMR data confirmed that this was an addition polymer. Example 219 Synthesis of 107 2,6-Dimethylthiophenol (3.0 g) waε mixed with 30 ml THF. Then 0.87g NaOH was added. The mixture was stirred until all the NaOH has diεεolved. THF waε removed under vacuum. To the solid was added 40 ml DMF and 4.02 g of the biε toluenesulfonate ester of ethylene glycol. The mixture waε refluxed for 5-6 h. DMF waε removed by rotary evaporator to give a white residue. Water was added to the reεidue and the mixture extracted with CH 2 C1 . After removing CH 2 C1 2 , a white εolid remained. TLC (hexane) showed two bandε. The second band from a silica-gel column waε the deεired produc . 1 H NMR (CDC1 3 , δ in ppm) : 2.43 (ε, 12H) ; 2.72(s, 4H) ; 7.10 (IT, 6H) . Example 220 Synthesis of 116 9-Anthraldehyde (2.06 g) was dissolved in a minimum amount of THF, then 1.37g anthranilic acid waε added. Four drops of formic acid were added aε catalyεt . The mixture was refluxed for 7h. TLC (5:1 hexane:ethyl acetate) gave 3 bandε. The second band lε the deεired product as determined by 1 H NMR. Example 221 Synthesis of 117 10-Chloro-9-anthraldehyde (2.41 g) was dissolved in a mixture of 30 ml THF/20 ml CDCl 3 /50 ml toluene. To this boiling solution waε added dropwise 3.5g 2,6-diisopropylaniline 3-4 drops of formic acid aε a catalyεt. The solution waε refluxed for 13h. After removing all the solvent, a dark brown thick oil was left. On standing, the oil cryεtallized. The cryεtals were washed with methane1. -" ■ H NMR (CDC1 3 , δ in ppm) : 1.40 (d, 12H) ; 3.35(p, 2H) ; • ?.40(m, 3H^ ; 7.75(m, 4H) ; 8.75(d, 2H) ; 9.05(d, 2H) ; 9.55(s, 1H) . Example 222 Synthesis of 118 10-Chloro-9-anthraldehyde waε (2.41 g) waε dissolved in 50 ml toluene, and to the hot solution was added 2.0 g of methyl anthranilate (m THF) dropwise. After refluxing for 6h, a yellow εolid precipitated. The εolid waε isolated by filtration, followed by washing with methanol. The solid was dissolved in 2- 3ml CDC1 3 and after column separation, golden yellow crystals were obtained. ^H NMR showed it is a pure product. X B NMR (DMF-d7, δ in ppm) : 4.20(ε, 3H) ; 6.50(d, 1H) ; 6.82 (t, 1H) ; 7.20 (t, 1H) ; 7.63 (t, 2H) ; 7.80(t, 2H) ; 8.10 (ε, 1H) ; 8.30 (d, 1H) ; 8.30 (d, 2H) ; 9.20 (d, 2H) . Example 223 In a dry and oxygen free atmosphere, the allyl initiator of Example 168 (16mg) waε dissolved in dry CH 2 C1 (2 ml) . Dicyclopentadiene (2 ml) waε added. The orange εolution darkened. After εtirring for 72 h the voiatiles were removed from the reaction under vacuum. After addition of methanol the solid polymer precipitated and waε filtered, washed well with methanol and dried. Yield = 0.29 g (15%) . The product waε insoluble at room temperature in common organic solventε.

Claims: CLAIMS What is claimed is : 1. A process for the polymerization of an olefin, comprising: (a) contacting a poly erizable monomer consisting essentially of ethylene, a norbornene or a styrene, and a catalyst system comprising the product of mixing in solution a zerovalent tricoordinate or tetracoordinate nickel compound (II) which has at least one labile ligand, and all ligands are neutral, an acid of the formula HX (IV) , and a first compound selected from the group consisting of: Ar 1 Qn (III) ; R 8 R 10 N-CR 4 R 5 (CR 6 R 7 ) m -NR 8 R 10 (V) ; H,N. H,N. ,P(OH) 2 * C0 2 H (XVIII) (XIX) ; OR" (XXIII ) ; - -NHAr" (XXVII ) ; R 22 R 23 R 24 p (χχvIII) . (XXXVI) and R ε S-CR R 5 (CR 6 R 7 ) m -SR ε (XXXVII) ; and wherein: X is a noncoordmatmg anion; Ar is an aromatic moiety with n free valencieε, or diphenylmethyl,- each Q lε -NR 2 R 43 or -CR 9 =NR 3 ; R 43 lε hydrogen or alkyl; n is 1 or 2 ; E lε 2-thιenyl or 2-furyl; 2 each R lε independently hydrogen, benzyl, εubεtituted benzy , phenyl or substituted phenyl; Q each R is independently hydrogen or hydrocarbyl,- and each R lε independently a monovalent aromatic moiety; each R , R , R , and R lε independently hydrogen, hydrocarbyl or substituted hydrocarbyl; each R is independently hydrocarbyl or substituted hydrocarbyl containing 2 or more carbon atoms; each R iε independently hydrogen, hydrocarbyl or substituted hydrocarbyl; Ar 2 is an aryl moiety; R 12 , R 13 , and R are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group; R 11 and R 15 are each independently hydrocarbyl, substituted hydrocarbyl or an inert functional group whose E s is about -0.4 or leεε; each R 16 and R 17 lε independently hydrogen or acyl containing l to 20 carbon atoms; Ar"* is an aryl moiety,- R 18 and R 19 are each independently hydrogen or hydrocarbyl,- Ar 4 is an aryl moiety; Ar 5 and Ar 6 are each independently hydrocarby; Ar' and Ar are each independently an aryl moiety,- 9 10 Ar and Ar are each independently an aryl moiety or -C0 2 R 2£ , wherein R 25 is alkyl containing 1 to 20 carbon atoms; Ar 11 lε an aryl moiety; R 41 lε hydrogen or hydrocarbyl; F 42 lε hydrocarbyl or -C(0) -NR 41 -Ar 1:l ,* R lε aryl ,- R 2 ~ and R are each independently phenyl groupε εubεtituted by one or more alkoxy groupε, each alkoxy group containing 1 to 20 carbon atoms,- and P "* is alkyl containing 1 to 20 carbon atoms, or an aryl moiety. 2 A catalyst for the polymerization of ethylene, a norbornene, or a styrene, comprising, the product of mixing solution a zerovalent tricoordinate or tetracoordinate nickel compound (II) which has at least one labile ligand and all ligands are neutral, an acid of the formula HX (IV) , and a firεt compound εelected from the group consisting of: r^-Qn (III) ; R 8 R 10 N-CR 4 R 5 (CR 6 R 7 ) m -NR 8 R 10 (V) ; (XXIII) (XXVI) ; Ar 9 HM S NHAr 1c (χχ V II) ; R 22 R 23 R 24 p (χχvIII) . (XXXVI) ; and R 6 S-CR 4 R 5 (CR 6 R 7 ) m -SR 8 (XXXVII) ; and wherein: X is a noncoordinating anion; Ar is an aromatic moiety with n free valencies, or diphenylmethyl,- each Q iε -NR 2 R 43 or -CR 9 =NR 3 ,- R 43 is hydrogen or alkyl n is 1 or 2; E is 2-thienyl or 2-furyl; 2 each R iε independently hydrogen, benzyl, substituted benzyl, phenyl or substituted phenyl,- each R is independently a monovalent aromatic moiety; q each R is independently hydrogen or hydrocarbyl; m is 1, 2 or 3; each R , R , R , and R is independently hydrogen, hydrocarbyl or substituted hydrocarbyl; p each P. is independently hydrocarbyl or substituted hydrocarbyl containing 2 or more carbon atoms,- each R is independently hydrogen, hydrocarbyl or substituted hydrocarbyl; Ar 2 is an aryl moiety; R 12 , R 1 , and R 14 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group; R 11 and R 15 are each independently hydrocarbyl, substituted hydrocarbyl or an inert functional group whose E s iε about -0.4 or leεε; each R 16 and R17 iε independently hydrogen or acyl containing 1 to 20 carbon atoms; Ar 3 is an aryl moiety; R lε and R 1S are each independently hydrogen or hydrocarbyl; Ar 4 iε an aryl moiety; Ar 5 and Ar are each independently hydrocarby; Ar' and Ar 8 are each independently an aryl moiety; Ar 5 and Ar 1 are each independently an aryl moiety, - C0 R *: ", or Ar' and Ar taken together are a divalent aromatic moiety and wherein R 25 iε alkyl containing 1 to 20 carbon atoms,- Ar 1- iε an aryl moiety; R 41 iε hydrogen or hydrocarbyl; R 42 iε hydrocarbyl or -C(O) -NR 41 -Ar 1:L ; R 22 and R 23 are each independently phenyl groups substituted by one or more alkoxy groups, each alkoxy group containing 1 to 20 carbon atomε; and R 24 is alkyl containing 1 to 20 carbon atoms, or an aryl moiety; R 44 is aryl; and provided that the molar ratio of (III) , (V) (XVI) , (XVII) , (XVIII), (XIX), (XX), (XXI), ( XXII ) , ( XXIII), ( XXIV ) , (XX V ), (XXVI), (XXVII) , (XXVIII), (XXXVI) or (XXXVII) : (II) iε about 0.5 to about 5, and the molar ratio of (IV) : (II) iε about 0.5 to about 10. 3. A process for the polymerization of an olefin, comprising, contacting ethylene, a norbornene, or a styrene with a nickel [II] complex of a firεt compound selected from the group consiεting of: Ar 1 Q n (III); R 8 R 10 N-CR 4 R 5 (CR 6 R 7 ) m -NR 8 R 10 (V) ; Ar ■ -NHR 1 C (XVI ) ; (XVI I ) ; (XXVI ) ; Ar 9 HN S NHAr 10 ( X χ V II ) R 22 R 23 R 24 p ( χχvI I I ) . (XXXVI) ; and R 8 S-CR 4 R 5 (CR 6 R 7 )π,-SR 8 (XXXVII); and wherein- X lε a noncoordmatmg anion; Ar lε an aromatic moiety with n free valencieε, or diphenylmethyl; each Q lε -NR 2 R 43 or -CR 9 =NR 3 ; R 4 " lε hydrogen or alkyl n lε 1 or 2,- E lε 2-thιenyl or 2-furyl; 2 each R lε independently hydrogen, benzyl, subεtituted benzyl, phenyl or substituted phenyl; each R is independently a monovalent aromatic moiety; each R is independently hydrogen or hydrocarbyl; m is 1, 2 or 3; each R , R , R , and R lε independently hydrogen, hydrocarbyl or substituted hydrocarbyl; Q each R is independently hydrocarbyl or substituted hydrocarbyl containing 2 or more carbon atoms; each R is independently hydrogen, hydrocarbyl or substituted hydrocarbyl,- Ar 2 is an aryl moiety; R 12 , R 1 , and R are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group; R 11 and R 15 are each independently hydrocarbyl, subεtituted hydrocarbyl or an inert functional group whoεe E s lε about -0.4 or leεε,- each R 16 and R17 is independently hydrogen or acyl containing l to 20 carbon atoms,* Ar 3 is an aryl moiety; R 1 and R ' are each independently hydrogen or hydrocarbyl,- Ar is an aryl moiety; Ar and Ar are each independently hydrocarby; 7 8 Ar and Ar are each independently an aryl moiety; Ar and Ar are each independently an aryl moiety, - C0 2 R 25 , or Ar 7 and Ar 8 taken together are a divalent aromatic 25 moiety and wherein R iε alkyl containing l to 20 carbon atoms,- Ar is an aryl moiety; R 41 iε hydrogen or hydrocarbyl; R 42 iε hydrocarbyl or -C(O) -NR 41 -Ar l:L ; R 44 iε aryl; 2- 3 R ' and R are each independently phenyl groupε substituted by one or more alkoxy groupε, each alkoxy group containing 1 to 20 carbon atoms, and R 24 ιε alkyl containing 1 to 20 carbon atomε, or an aryl moiety. 4. A process for the polymerization of olefinε, compriεing, contacting ethylene, a norbornene or a styrene with a nickel containing first compound of the formula [L q L r L s L 4 t Ni] + X ~ (XXXIII) , wherein: L' iε a firεt monodentate neutral ligand coordinated to said nickel, L 2 is a second monodentate neutral ligand coordinated to said nickel which may be εaid firεt monodentate neutral ligand and r iε 0 or 1, or L 1 and L2 taken together are a firεt bidentate neutral ligand coordinated to said nickel and r iε 1; L 3 and L 4 taken together are a π-allyl ligand coordinated to εaid nickel, h" and L taken together are (XXXII ) coordinated to said nickel, or L is a third neutral monodentate ligand selected from the group consisting of ethylene, a norbornene and a styrene or a neutral monodentate ligand which can be displaced by an olefin, and L 4 is R 38 ,* q, s and t are each 1; X iε a relatively non- coordinating anion; said first monodentate neutral ligand and said first bidentate neutral ligand are selected from the group consisting of Ar 1 Q n (III); R 8 R 10 N-CR 4 R 5 (CR 6 R 7 ) m -NR 8 R 10 (V) ; Ar- -NHR 1 ' (XVI) ; (XVII) ; (XXIII ; ; (XXVI) ; Ar 9 HN S NHAr 0 (χχvil) ; R 22 R 23 R 24 p ( χχvI I I ) . (XXXVI ) ; and R E S-CR 4 R 5 (CR 6 R 7 ) m -SR B (XXXVII); Ar is an aromatic moiety with n free valencies, or diphenylmethyl,- each Q iε -NR 2 R 43 or -CR 9 =NR 3 ; R 43 iε hydrogen or alkyl n iε 1 or 2; E iε 2-thienyl or 2-furyl; 2 each R iε independently hydrogen, benzyl, substituted benzyl, phenyl or subεtituted phenyl; q each R iε independently hydrogen or hydrocarbyl; and each R iε independently a monovalent aromatic moiety; m iε 1, 2 or 3; each R , R , R , and R iε independently hydrogen, hydrocarbyl or εubεtituted hydrocarbyl; p each R iε independently hydrocarbyl or subεtituted hydrocarbyl containing 2 or more carbon atoms; each R iε independently hydrogen, hydrocarbyl or εubstituted hydrocarbyl; Ar ^ is an aryl moiety; R 1^ , R lj , and R are each independently hydrogen, hydrocarbyl, subεtituted hydrocarbyl or an inert functional group; R 11 and R 1 " are each independently hydrocarbyl, εubεtituted hydrocarbyl or an inert functional group whose E s iε about -0.4 or leεε; each R 16 and R 1 iε independently hydrogen or acyl containing 1 to 20 carbon atomε; Ar 3 iε an aryl moiety; R 18 and R 19 are each independently hydrogen or hydrocarbyl,- Ar 4 iε an aryl moiety; Ar 5 and Ar are each independently hydrocarby; Ar 7 and Ar8 are each independently an aryl moiety; Ar 9 and Ar are each independently an aryl moiety or -C0 2 R 25 , wherein R 25 is alkyl containing 1 to 20 carbon atoms; Ar 11 iε an aryl moiety; R 41 iε hydrogen or hydrocarbyl; R 42 is hydrocarbyl or -C(0) -NR 1 -Ar l:L ; R" and R" J are each independently phenyl groupε εubεtituted by one or more alkoxy groupε, each alkoxy group containing l to 20 carbon atoms; and R 24 iε alkyl containing 1 to 20 carbon atomε, or an aryl moiety; R 35 is hydrocarbylene; R 36 is hydrogen, alkyl, or -C(0)R 39 ,- each R 37 is hydrocarbyl or both of R 37 taken together are hydrocarbylene to form a carbocyclic ring; R 38 is hydride, alkyl or -C(0)R 3S ; R 3 is hydrocarbyl,- and R 44 iε aryl. 5 . A compound of the formula [L 1 q L 2 r L 3 E L 4 t Ni] + X " (XXXIII ) , wherei : L 1 is a first monodentate neutral ligand coordinated to said nickel, L 2 iε a second monodentate neutral ligand coordinated to said nickel which may be said firεt monodentate neutral ligand and r s 0 or 1, or L 1 and L2 taken together are a firεt bidentate neutral ligand coordinated to εaid nickel and r iε 1; L J and L taken together are a π-allyl ligand coordinated to εaid nickel, L" and L taken together are (XXXII) coordinated to said nickel, or L is a third neutral monodentate ligand selected from the group consisting of ethylene, a norbornene and a styrene or a neutral monodentate ligand which can be displaced by an olefin, and L 4 is R ,- X iε a relatively non-coordinating anion; g, s and t are each 1; said first monodentate neutral ligand and said first bidentate neutral ligand are selected from the group consisting of Ar^ (III); R 8 R 10 N-CR 4 R 5 (CR 6 R 7 ) m -NR 8 R 10 (V) ; H,N, H,N, ,P(OH) 2 * C0 2 H (XVIII) (XIX) ; (XXIII) (XXVI) ; Ar 9 HN S NHAr 10 (χχvil) R 22 R 23 R 24 P (XXVIII) ; (XXXVI) and R 8 S-CR 4 R 5 (CR 6 R 7 ) m -SR 8 (XXXVII) ; Ar is an aromatic moiety with n free valencies, or diphenylmethyl,- each Q is -NR 2 R 43 or -CR 9 =NR 3 ; R 43 is hydrogen or alkyl n is l or 2,- E is 2-thienyl or 2-furyl; 2 each R is independently hydrogen, benzyl, substituted benzyl, phenyl or substituted phenyl,* q each R iε independently hydrogen or hydrocarbyl; and each R is independently a monovalent aromatic moiety; m is 1, 2 or 3; each R , R , R , and R is independently hydrogen, hydrocarbyl or substituted hydrocarbyl; p each R is independently hydrocarbyl or substituted hydrocarbyl containing 2 or more carbon atoms,- each R iε independently hydrogen, hydrocarbyl or εubεtituted hydrocarbyl; Ar 2 iε an aryl moiety; R 12 , R 13 , and R 1 are each independently hydrogen, hydrocarbyl, subεtituted hydrocarbyl or an inert functional group; R 11 and R 1 are each independently hydrocarbyl, εubεtituted hydrocarbyl or an inert functional group whoεe E s iε about -0.4 or leεε; each R and R iε independently hydrogen or acyl containing 1 to 20 carbon atomε; Ar 3 is an aryl moiety; R 18 and R are each independently hydrogen or hydrocarbyl; Ar iε an aryl moiety; Ar and Ar are each independently hydrocarby; Ar and Ar are each independently an aryl moiety; Ar 9 and Ar10 are each independently an aryl moiety or -Cθ 2 R 5 , wherein R is alkyl containing 1 to 20 carbon atoms,- Ar 11 is an aryl moiety; R 41 is hydrogen or hydrocarbyl; R 42 is hydrocarbyl or -C(θ) -NR 41 -Ar ια ; R is aryl; R" and R 3 are each independently phenyl groupε εubεtituted by one or more alkoxy groupε, each alkoxy group containing l to 20 carbon atoms,- and R 24 is alkyl containing l to 20 carbon atomε, or an aryl moiety, R 35 lε hydrocarbylene; R 3€ lε hydrogen, alkyl, or -C(θ)R 39 ; each R 37 lε hydrocarbyl or both of R 3 taken together are hydrocarbylene to form a carbocyclic ring; R 38 lε hydride, alkyl or -C(0)R 39 ,* and R 3S ιε hydrocarbyl 6 The proceεε aε recited m claim l or 3 wherein the molar ratio of (III) (II) lε about 0.5 to 5, and the molar ratio of (IV) (II) is about 0.5 to about 10. 7 The process or catalyst aε recited in claim 1, 2, 3, 4 or 5 wherein X lε BF 4 " , PF 6 ~, BAF"' or SbF 6 ~ 8 The proceεε or catalyεt aε recited in claim 1, 2 or 3 wherein (II) is biε(η 4 -l,5-cyclooctadienyl)nickel [0] . 9 The process as recited in claim 1, 3 or 4 wherein an olefm is ethylene 10 The procesε aε recited in claim 1, 3 or 4 wherein an olefin is norbornene 11 The procesε aε recited in claim 1, 3 or 4 wherein an olefin is styrene. 12 The procesε as recited m claim 1, 3 or 4 wherein an olefin is a combination of styrene and norbornene, and a copolymer of styrene and norbornene is produced 13 The procesε, compound or catalyεt aε recited m claim 1, 2, 3, 4 or 5 wherein sa d first compound or said first monodentate neutral ligand is (III) . 14. The process, compound or catalyst as recited in claim 13 wherein- n is 1, Q is -CR 9 =NR 3 , R 9 is hydrogen, Ar 1 is 9- anthracenyl, and R 3 is -carbamoylphenyl or 2,6-dnsopropylphenyl; 9 3 3 n is 2 and Q is -CR =NR , R is 2,6-dιsubstιtuted phenyl in which substitutents are halo, alkyl, or halo and alkyl, Ar 1 is 9 p-phenylene, and R lε hydrogen,- n is 1, Q is -CR 9 =NR 3 , R 9 lε hydrogen, R 3 lε 2,6- dimethylphenyl, and Ar is pentafluorophenyl; or n is 1, 0 is -CR 9 =NR 3 , R s is hydrogen, R 3 is 2,6- dnεopropylphenyl, and Ar 1 is 2-hydroxy-l-naphthyl. 15 The process, compound or catalyst as recited in claim 13 wherein n is 1, Q lε -NR 2 R 43 , R 2 lε -CH=CPh 2 , R 43 lε hydrogen, and Ar 1 is 2, 6-dιιsopropylphenyl, nn liεs 1l,, QQ 1l8ε --NNR 2 R 43 , R 2 is -CH=CPh 2 , R 43 lε hydrogen and Ar 1 is 2-carbamoylphenyl; n lε 2, Q is -NR R 4 , R 2 is hydrogen, R 43 is hydrogen, and Ar 1 is l,8-napthylylene; n lε l, Q is -NR R 43 , R 2 lε -CH=CPh 2 , R 43 is hydrogen, and Ar 1 is 2-methoxycarbonylphenyl; n is 1, Q is -NR R 4 , R 2 is hydrogen, R 43 is hydrogen, and Ai 1 is 2-carboxyphenyl, n lε 1, Q is -NR 2 R 43 , R 2 is -CH=CPh 2 , R 43 lε hydrogen, and Ar lε 1-anthragumonyl, n lε 1, Q lε NR 2 R 43 , R 2 is -CH=CPh 2 , R 43 is hydrogen, and Ar is 16 The proceεε, compound or catalyst as recited in claim 1, 2, 3, 4 or 5 wherein said first compound or said first monodentate neutral ligand s (V) . 17 The process or catalyst as recited in claim 16 wherein: m is 1, all of R , R , R , R an R are hydrogen, and both of R 10 are 2,6-dnsopropylphenyl; or m s 1, all of R , R , R , R an R 7 are hydrogen, and both of R 1 are cyclohexyl. 18 The procesε, compound or catalyst as recited in claim 1, 2, 3, 4 or 5 wherein said first compound or said first monodentate neutral ligand is (XVI) 19 The proceεε or catalyεt aε recited in claim 18 wherein Ar 2 lε 2- (N-2,2-diphenylethenylam o)phenyl and R 1C lε hydrogen, 2 10 Ar lε phenyl and R is 2,6-dιιsopropylphenyl, Ar 2 is 2-pyrιdyl and R is hydrogen, or Ar 2 is 3-hydroxy-2-pyrιdyl and R lc is hydrogen 20 The procesε, compound or catalyst as recited n claim 1, 2, 3, 4 or 5 wherein said first compound or said first monodentate neutral ligand is (XVII) . 21 The procesε, compound or catalyst aε recited in claim 20 wherein P 11 and R 15 are t-butyl and R 12 , R 13 and R 14 are hydrogen, R 11 , R 13 and R 15 are t-butyl and R 12 and R 14 are hydrogen, R 1 " and R 15 are phenyl and R 12 , R 13 and R 14 are hydrogen, or R 11 ιε t-butyl and R 12 and R 14 are hydrogen, R 13 lε methoxy, and R 15 lε 2-hydroxy-3-t-butyl-5-methoxyphenyl 22 The proceεε, compound or catalyst as recited in claim 1, 2, 3, 4 or 5 wherein said first compound or said first monodentate neutral ligand is (XVIII) 23 The process, compound or catalyst as recited in claim 1, 2, 3, 4 or 5 wherein said first compound or said first monodentate neutral ligand is (XIX) 24 The proceεε, compound or catalyεt aε recited in claim 1, 2, 3, 4 or 5 wherein said first compound or said first monodentate neutral ligand is (XX) both of R are phenyl. 25 The process, compound or catalyεt as recited in claim 24 wherein both of R 1 and R are hydrogen; or both of R 16 and R 17 are acetyl 26 The process, compound or catalyst as recited in claim 1, 2, 3, 4 or 5 wherein said first compound or said first monodentate neutral ligand is (XXI) . 27. The process, compound or catalyst as recited in claim 26 wherein Ar 3 is 2-aminophenyl. 28. The procesε, compound or catalyst as recited m claim 1, 2, 3, 4 or 5 wherein said first compound or said first monodentate neutral ligand is (XXII) . 29 The procesε, compound or catalyst as recited in claim 28 wherein R 1E and R 19 are both methyl or both hydrogen 30 The procesε, compound or catalyst as recited in claim 1, 2, 3 , 4 or 5 wherein said first compound or said first monodentate neutral ligand is (XXIII) . 31. The process, compound or catalyst as recited in claim 30 wherein Ar 4 is phenyl. 32. The process, compound or catalyst as recited in claim 1, 2, 3, 4 or 5 wherein said first compound or said first monodentate neutral ligand is (XXIV) . 33. The process, compound or catalyst aε recited m claim 32 wherein both of Ar 5 and Ar are phenyl or wherein both of Ar 5 and Ar are cyclohexyl 34 The procesε, compound or catalyst aε recited in claim 1, 2, 3, 4 or 5 wherein said first compound or said first monodentate neutral ligand is (XXV) 35 The proceεε, compound or catalyst as recited m claim 1, 2, 3 , 4 or 5 wherein said first compound or said first monodentate neutral ligand is (XXVI) . 36 The proceεs, compound or catalyst as recited in claim 35 wherein Ar 7 is p-tolyl or phenyl and Arθ is 2,6-dιιsopropylphenyl 3"? The procesε, compound or catalyst as recited in claim 1, 2, 3, 4 or 5 wherein said first compound or said first monodentate neutral ligand is (XXVII) . 36 Tne procesε, compound or catalyst as recited in claim 37 wherein Ar and Ar taken together are 1,8-naphthylylene; or Ar 9 is -C0 2 CH 3 and Ar lc is 39. The procesε, compound or catalyst as recited in claim 1, 2, 3, 4 or 5 wherein said first compound or said first monodentate neutral ligand iε (XXVIII) . 40. The process, compound or catalyst as recited in claim 39 wherein: all of R 22 , R 23 and R 24 are 2,4,6-trimethoxyphenyl; both of R 22 and R are 2, 3,6-trimethoxyphenyl and R 24 iε ethyl,- all of R 22 , R 23 and R are 2, 6-dimethoxyphenyl; or both of R 22 and R 23 are 2,3,6-trimethoxyphenyl and R 24 is isopropyl . 41. The procesε, compound or catalyst as recited in claim 39 wherein at least one of R , R and R is substituted and that a sum of σ and σ* constantε for at leaεt one of R 22 , R 23 and R 24 is about -0.50 or less. 42. The process, compound or catalyst aε recited in claim 41 wherein R 24 iε an aryl moiety, all of R , R and R are substituted, and said sum of said σ and σ* constants for each of R 2 , R 2j and R 24 iε about -0.50 or less. 43. A compound of the formula (XXIV) wherein: E iε 2-thienyl or 2-furyl; Ar 5 and Ar are each independently hydrocarby. 4 . The compound aε recited in claim 43 wherein both of Ar and A.r are phenyl or wherein both of Ar and Ar are cyclohexyl . 45. The process as recited in claim 3 or 4 carried out in a solvent . 46. The process as recited in claim 1, 3 or 4 carried out at a temperature of about -20°C to about 100°C. 47. The proceεε, compound or catalyst as recited in claim 1, 2, 3., 4 or 5 wherein said first compound or said first monodentate neutral ligand is (XXXVI) . 48. The process, compound or catalyst as recited in claim l, 2, 3, 4 or 5 wherein (XXXVI) is 49. The process, compound or catalyst as recited in claim l, 2, 3, 4 or 5 wherein said first compound or said first monodentate neutral ligand is (XXXVII) . 50. The process, compound or catalyst as recited in claim 49 wherein both of R 8 are aryl moieties and all of R 4 , R 5 , R 6 , R 7 and R 8 are hydrogen. 51.The process as recited in claim 50 wherein both of R 8 are 2,6-dimethylphenyl. 52. The process, compound or catalyst as recited in claim l, 2, 3, 4 or 5 wherein X is BAF. 53. The process or compound as recited in claim 4 or 5 wherein r is 1. 54. The process or compound as recited in claim 4 or 5 wherein r is 0. 55. The process or compound as recited in claim 54 wherein (XXXIII) is a dimer with bridging L ligands. 56. The process, compound or catalyst as recited in claim 13 wherein-. n is 2 Q is -CR 9 =NR 3 ; Ar 1 iε diphenylmethyl;R iε hydrogen and R iε selected from the group consisting of 2,6- diisopropylphenyl, 2-carbamoylphenyl, 2-methoxycarbonylphenyl, 1- anthraquinolyl, 2,6-dimethylphenyl and l-fluoren-9-onyl. 57. The process as recited in claim 3 wherein said nickel [II] complex is a π-allyl complex. 58. The process as recited in claim 4 wherein L and L 4 taken together are a π-allyl group. 59. The compound as recited in claim 5 wherein L and L 4 taken together are a π-allyl group. 60. The process as recited in claim 57 or 58 wherein a Lewis acid is also present. 61. The process as recited 1, 3 or 4 wherein at least 2 or more norbomenes are present, to form a copolymer. 62. The process as recited in claim 1, 3 or 4 wherein at least 2 or more styreneε are present to form a copolymer. 63. The process as recited in claim 1, 3 or 4 wherein at least one styrene and at least norbornene are present to form a copolymer. 64. The process as recited in claim 61 wherein a nobomene present is 5-ethylidene-2-norbonene.

Inventors: BENNETT ALISON MARGARET ANNE, COUGHLIN EDWARD BRYAN, DONALD DENNIS SCOTT, FELDMAN JERALD, JOHNSON LYNDA KAYE, KREUTZER KRISTINA ANN, MCLAIN STEPHAN JAMES, NELSON LISSA TAKA JENNINGS, PARTHASARATHY ANJU, SHEN XING, TAM WILSON, WANG YUELI, BENNETT, ALISON, MARGARET, ANNE, COUGHLIN, EDWARD, BRYAN, DONALD, DENNIS, SCOTT, FELDMAN, JERALD, JOHNSON, LYNDA, KAYE, KREUTZER, KRISTINA, ANN, MCLAIN, STEPHAN, JAMES, NELSON, LISSA, TAKA, JENNINGS, PARTHASARATHY, ANJU, SHEN, XING, TAM, WILSON, WANG, YUELI
Applicants: BENNETT ALISON MARGARET ANNE, COUGHLIN EDWARD BRYAN, DONALD DENNIS SCOTT, DU PONT, FELDMAN JERALD, JOHNSON LYNDA KAYE, KREUTZER KRISTINA ANN, MCLAIN STEPHAN JAMES, NELSON LISSA TAKA JENNINGS, PARTHASARATHY ANJU, SHEN XING, TAM WILSON, WANG YUELI, BENNETT, ALISON, MARGARET, ANNE, COUGHLIN, EDWARD, BRYAN, DONALD, DENNIS, SCOTT, E.I. DU PONT DE NEMOURS AND COMPANY, FELDMAN, JERALD, JOHNSON, LYNDA, KAYE, KREUTZER, KRISTINA, ANN, MCLAIN, STEPHAN, JAMES, NELSON, LISSA, TAKA, JENNINGS, PARTHASARATHY, ANJU, SHEN, XING, TAM, WILSON, WANG, YUELI
Application year: 1996
Main classification: C08F10
IPC codes: C07F15, C08F4, C08F10, C08F12, C08F32, C08F36, C08F110, C08F210