Olefin polymerization process

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 coordinated to the nickel with the olefin(s). The polymers produced are useful for films and molding resins.

This application is a continuation-in-part of U.S. provisional application 
Ser. No. 60/000,747, filed Jun. 30, 1995. 
FIELD OF THE INVENTION 
This invention concerns a process for the preparation of polyolefins by 
coordination polymerization of ethylene, styrene or norbornene by a nickel 
compound coordinated to a selected ligand. 
TECHNICAL BACKGROUND 
Polyolefins 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 olefins 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 olefin 
polymerization catalyst usually depends on the metal chosen and what 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. Other factors such as the efficiency and rate 
of polymerization may vary. Therefore, new transition metal catalysts for 
olefin polymerizations are constantly being sought. 
SUMMARY OF THE INVENTION 
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: 
##STR1## 
wherein: 
X is a noncoordinating anion; 
Ar.sup.1 is an aromatic moiety with n free valencies, or diphenylmethyl; 
each Q is --NR.sup.2 R.sup.43 or --CR.sup.9 =NR.sup.3 ; 
n is 1 or 2; 
E is 2-thienyl or 2-furyl; 
each R.sup.2 is independently hydrogen, benzyl, substituted benzyl, phenyl 
or substituted phenyl; 
each R.sup.9 is independently hydrogen or hydrocarbyl; and 
each R.sup.3 is independently a monovalent aromatic moiety; 
m is 1, 2 or 3; 
R.sup.43 is hydrogen or alkyl; 
each R.sup.4, R.sup.5, R.sup.6, R.sup.7 is independently hydrogen, 
hydrocarbyl or substituted hydrocarbyl; 
each R.sup.8 is independently hydrocarbyl or substituted hydrocarbyl 
containing 2 or more carbon atoms; 
each R.sup.10 is independently hydrogen, hydrocarbyl or substituted 
hydrocarbyl; 
Ar.sup.2 is an aryl moiety; 
R.sup.12, R.sup.13, and R.sup.14 are each independently hydrogen, 
hydrocarbyl, substituted hydrocarbyl or an inert functional group; 
R.sup.11 and R.sup.15 are each independently hydrocarbyl, substituted 
hydrocarbyl or an inert functional group whose E.sub.s is about -0.4 or 
less; 
each R.sup.16 and R.sup.17 is independently hydrogen or acyl containing 1 
to 20 carbon atoms; 
Ar.sup.3 is an aryl moiety; 
R.sup.18 and R.sup.19 are each independently hydrogen or hydrocarbyl; 
Ar.sup.4 is an aryl moiety; 
Ar.sup.5 and Ar.sup.6 are each independently hydrocarbyl; 
Ar.sup.7 and Ar.sup.8 are each independently an aryl moiety; 
Ar.sup.9 and Ar.sup.10 are each independently an aryl moiety or --CO.sub.2 
R.sup.25, wherein R.sup.25 is alkyl containing 1 to 20 carbon atoms; 
Ar.sup.11 is an aryl moiety; 
R.sup.41 is hydrogen or hydrocarbyl; 
R.sup.42 is hydrocarbyl or --C(O)--NR.sup.41 --Ar.sup.11 ; 
R.sup.44 is aryl; 
R.sup.22 and R.sup.23 are each independently phenyl groups substituted by 
one or more alkoxy groups, each alkoxy group containing 1 to 20 carbon 
atoms; and 
R.sup.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 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 compound selected from the group consisting of: 
##STR2## 
wherein: 
X is a noncoordinating anion; 
Ar.sup.1 is an aromatic moiety with n free valencies, or diphenylmethyl; 
each Q is --NR.sup.2 R.sup.43 or --CR.sup.9 =NR.sup.3 ; 
n is 1 or 2; 
E is 2-thienyl or 2-furyl; 
R.sup.43 is hydrogen or alkyl; 
each R.sup.2 is independently hydrogen, benzyl, substituted benzyl, phenyl 
or substituted phenyl; 
each R.sup.3 is independently a monovalent aromatic moiety; 
each R.sup.9 is independently hydrogen or hydrocarbyl; 
m is 1, 2 or 3; 
each R.sup.4, R.sup.5, R.sup.6, and R.sup.7 is independently hydrogen, 
hydrocarbyl or substituted hydrocarbyl; 
each R.sup.8 is independently hydrocarbyl or substituted hydrocarbyl 
containing 2 or more carbon atoms; 
each R.sup.10 is independently hydrogen, hydrocarbyl or substituted 
hydrocarbyl; 
Ar.sup.2 is an aryl moiety; 
R.sup.12, R.sup.13, and R.sup.14 are each independently hydrogen, 
hydrocarbyl, substituted hydrocarbyl or an inert functional group; 
R.sup.11 and R.sup.15 are each independently hydrocarbyl, substituted 
hydrocarbyl or an inert functional group whose E.sub.s is about -0.4 or 
less; 
each R.sup.16 and R.sup.17 is independently hydrogen or acyl containing 1 
to 20 carbon atoms; 
Ar.sup.3 is an aryl moiety; 
R.sup.16 and R.sup.19 are each independently hydrogen or hydrocarbyl; 
Ar.sup.4 is an aryl moiety; 
Ar.sup.5 and Ar.sup.6 are each independently hydrocarby; 
Ar.sup.7 and Ar.sup.8 are each independently an aryl moiety; 
Ar.sup.9 and Ar.sup.10 are each independently an aryl moiety, CO.sub.2 
R.sup.25, or Ar.sup.7 and Ar.sup.8 taken together are a divalent aromatic 
moiety, and wherein R.sup.25 is alkyl containing 1 to 20 carbon atoms; 
Ar.sup.11 is an aryl moiety; 
R.sup.41 is hydrogen or hydrocarbyl; 
R.sup.42 is hydrocarbyl or --C(O)--NR.sup.41 --Ar.sup.11 ; 
R.sup.44 is aryl; 
R.sup.22 and R.sup.23 are each independently phenyl groups substituted by 
one or more alkoxy groups, each alkoxy group containing 1 to 20 carbon 
atoms; and 
R.sup.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: 
##STR3## 
wherein: 
X is a noncoordinating anion; 
Ar.sup.1 is an aromatic moiety with n free valencies, or diphenylmethyl; 
each Q is --NR.sup.2 R.sup.43 or --CR.sup.9 =NR.sup.3 ; 
R.sup.43 is hydrogen or alkyl; 
n is 1 or 2; 
E is 2-thienyl or 2-furyl; 
each R.sup.2 is independently hydrogen, benzyl, substituted benzyl, phenyl 
or substituted phenyl; 
each R.sup.3 is independently a monovalent aromatic moiety; 
each R.sup.9 is independently hydrogen or hydrocarbyl; m is 1, 2 or 3; 
each R.sup.4, R.sup.5, R.sup.6, and R.sup.7 is independently hydrogen, 
hydrocarbyl or substituted hydrocarbyl; 
each R.sup.8 is independently hydrocarbyl or substituted hydrocarbyl 
containing 2 or more carbon atoms; 
each R.sup.10 is independently hydrogen, hydrocarbyl or substituted 
hydrocarbyl; 
Ar.sup.2 is an aryl moiety; 
R.sup.12, R.sup.13, and R.sup.14 are each independently hydrogen, 
hydrocarbyl, substituted hydrocarbyl or an inert functional group; 
R.sup.11 and R.sup.15 are each independently hydrocarbyl, substituted 
hydrocarbyl or an inert functional group whose E.sub.s is about -0.4 or 
less; 
each R.sup.16 and R.sup.17 is independently hydrogen or acyl containing 1 
to 20 carbon atoms; 
Ar.sup.3 is an aryl moiety; 
R.sup.18 and R.sup.19 are each independently hydrogen or hydrocarbyl; 
Ar.sup.4 is an aryl moiety; 
Ar.sup.5 and Ar.sup.6 are each independently hydrocarby; 
Ar.sup.7 and Ar.sup.8 are each independently an aryl moiety; 
Ar.sup.9 and Ar.sup.10 are each independently an aryl moiety, CO.sub.2 
R.sup.25, or Ar.sup.7 and Ar.sup.8 taken together are a divalent aromatic 
moiety and wherein R.sup.25 is alkyl containing 1 to 20 carbon atoms; 
Ar.sup.11 is an aryl moiety; 
R.sup.41 is hydrogen or hydrocarbyl; 
R.sup.42 is hydrocarbyl or --C(O)--NR.sup.41 Ar.sup.11 ; 
R.sup.44 is aryl; 
R.sup.22 and R.sup.23 are each independently phenyl groups substituted by 
one or more alkoxy groups, each alkoxy group containing 1 to 20 carbon 
atoms; and 
R.sup.24 is alkyl containing 1 to 20 carbon atoms, or an aryl moiety. 
Described herein is a process for the polymerization of olefins, 
comprising, contacting ethylene, a norbornene or a styrene with a nickel 
containing first compound of the formula L.sup.1.sub.q L.sup.2.sub.r 
L.sup.3.sub.s L.sup.4.sub.t Ni!.sup.+ X.sup.- (XXXIII), wherein: 
L.sup.1 is a first monodentate neutral ligand coordinated to said nickel, 
L.sup.2 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 
L.sup.1 and L.sup.2 taken together are a first bidentate neutral ligand 
coordinated to said nickel and r is 1; 
L.sup.3 and L.sup.4 taken together are a .pi.-allyl ligand coordinated to 
said nickel, L.sup.3 and L.sup.4 taken together are 
##STR4## 
coordinated to said nickel, or L.sup.3 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.sup.4 is R.sup.38 ; 
X is a relatively non-coordinating anion; 
each of q, s and t is 1; 
said first monodentate neutral ligand and said first bidentate neutral 
ligand are selected from the group consisting of 
##STR5## 
Ar.sup.1 is an aromatic moiety with n free valencies, or diphenylmethyl; 
each Q is --NR.sup.2 R.sup.43 or --CR.sup.9 =NR.sup.3 ; 
R.sup.43 is hydrogen or alkyl; 
n is 1 or 2; 
E is 2-thienyl or 2-furyl; 
each R.sup.2 is independently hydrogen, benzyl, substituted benzyl, phenyl 
or substituted phenyl; 
each R.sup.9 is independently hydrogen or hydrocarbyl; and 
each R.sup.3 is independently a monovalent aromatic moiety; 
m is 1, 2 or 3; 
each R.sup.4, R.sup.5, R.sup.6, and R.sup.7 is independently hydrogen, 
hydrocarbyl or substituted hydrocarbyl; 
each R.sup.8 is independently hydrocarbyl or substituted hydrocarbyl 
containing 2 or more carbon atoms; 
each R.sup.10 is independently hydrogen, hydrocarbyl or substituted 
hydrocarbyl; 
Ar.sup.2 is an aryl moiety; 
R.sup.12, R.sup.13, and R.sup.14 are each independently hydrogen, 
hydrocarbyl, substituted hydrocarbyl or an inert functional group; 
R.sup.11 and R.sup.15 are each independently hydrocarbyl, substituted 
hydrocarbyl or an inert functional group whose E.sub.s is about -0.4 or 
less; 
each R.sup.16 and R.sup.17 is independently hydrogen or acyl containing 1 
to 20 carbon atoms; 
Ar.sup.3 is an aryl moiety; 
R.sup.18 and R.sup.19 are each independently hydrogen or hydrocarbyl; 
Ar.sup.4 is an aryl moiety; 
Ar.sup.5 and Ar.sup.6 are each independently hydrocarby; 
Ar.sup.7 and Ar.sup.8 are each independently an aryl moiety; 
Ar.sup.9 and Ar.sup.10 are each independently an aryl moiety or --CO.sub.2 
R.sup.25, wherein R.sup.25 is alkyl containing 1 to 20 carbon atoms; 
Ar.sup.11 is an aryl moiety; 
R.sup.41 is hydrogen or hydrocarbyl; 
R.sup.42 is hydrocarbyl or --C(O)--NR.sup.41 --Ar.sup.11 ; 
R.sup.22 and R.sup.23 are each independently phenyl groups substituted by 
one or more alkoxy groups, each alkoxy group containing 1 to 20 carbon 
atoms; and 
R.sup.24 is alkyl containing 1 to 20 carbon atoms, or an aryl moiety; 
R.sup.35 is hydrocarbylene; 
R.sup.36 is hydrogen, alkyl, or --C(O)R.sup.39 ; 
each R.sup.37 is hydrocarbyl or both of R.sup.37 taken together are 
hydrocarbylene to form a carbocyclic ring; 
R.sup.38 is hydride, alkyl or --C(O)R.sup.39 ; and 
R.sup.39 is hydrocarbyl 
R.sup.44 is aryl. 
Also described herein is a compound of the formula L.sup.1.sub.q 
L.sup.2.sub.r L.sup.3.sub.s L.sup.4.sub.t Ni!.sup.+ X.sup.- (XXXIII), 
wherein: 
L.sup.1 is a first monodentate neutral ligand coordinated to said nickel, 
L.sup.2 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 
L.sup.1 and L.sup.2 taken together are a first bidentate neutral ligand 
coordinated to said nickel and r is 1; 
L.sup.3 and L.sup.4 taken together are a .pi.-allyl ligand coordinated to 
said nickel, L.sup.3 and L.sup.4 taken together are 
##STR6## 
coordinated to said nickel, or L.sup.3 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.sup.4 is R.sup.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 
##STR7## 
wherein: 
Ar.sup.1 is an aromatic moiety with n free valencies, or diphenylmethyl; 
each Q is --NR.sup.2 R.sup.43 or --CR.sup.9 =NR.sup.3 ; 
R.sup.43 is hydrogen or alkyl; 
n is 1 or 2; 
E is 2-thienyl or 2-furyl; 
each R.sup.2 is independently hydrogen, benzyl, substituted benzyl, phenyl 
or substituted phenyl; 
each R.sup.9 is independently hydrogen or hydrocarbyl; and 
each R.sup.3 is independently a monovalent aromatic moiety; 
m is 1, 2 or 3; 
each R.sup.4, R.sup.5, R.sup.6, and R.sup.7 is independently hydrogen, 
hydrocarbyl or substituted hydrocarbyl; 
each R.sup.8 is independently hydrocarbyl or substituted hydrocarbyl 
containing 2 or more carbon atoms; 
each R.sup.10 is independently hydrogen, hydrocarbyl or substituted 
hydrocarbyl; 
Ar.sup.2 is an aryl moiety; 
R.sup.12, R.sup.13, and R.sup.14 are each independently hydrogen, 
hydrocarbyl, substituted hydrocarbyl or an inert functional group; 
R.sup.11 and R.sup.15 are each independently hydrocarbyl, substituted 
hydrocarbyl or an inert functional group whose E.sub.s is about -0.4 or 
less; 
each R.sup.16 and R.sup.17 is independently hydrogen or acyl containing 1 
to 20 carbon atoms; 
Ar.sup.3 is an aryl moiety; 
R.sup.16 and R.sup.19 are each independently hydrogen or hydrocarbyl; 
Ar.sup.4 is an aryl moiety; 
Ar.sup.5 and Ar.sup.6 are each independently hydrocarby; 
Ar.sup.7 and Ar.sup.8 are each independently an aryl moiety; 
Ar.sup.9 and Ar.sup.10 are each independently an aryl moiety or --CO.sub.2 
R.sup.25, wherein R.sup.25 is alkyl containing 1 to 20 carbon atoms; 
Ar.sup.11 is an aryl moiety; 
R.sup.41 is hydrogen or hydrocarbyl; 
R.sup.42 is hydrocarbyl or --C(O)--NR.sup.41 --Ar.sup.11 ; 
R.sup.44 is aryl; 
R.sup.22 and R.sup.23 are each independently phenyl groups substituted by 
one or more alkoxy groups, each alkoxy group containing 1 to 20 carbon 
atoms; and 
R.sup.24 is alkyl containing 1 to 20 carbon atoms, or an aryl moiety; 
R.sup.35 is hydrocarbylene; 
R.sup.36 is hydrogen, alkyl, or --C(O)R.sup.39 ; 
each R.sup.37 is hydrocarbyl or both of R.sup.37 taken together are 
hydrocarbylene to form a carbocyclic ring; 
R.sup.38 is hydride, alkyl or --C(O)R.sup.39 ; and 
R.sup.39 is hydrocarbyl. 
Described herein is a compound of the formula 
##STR8## 
wherein: 
E is 2-thienyl or 2-furyl; 
Ar.sup.5 and Ar.sup.6 are each independently hydrocarby. 
DETAILS OF THE INVENTION 
The olefins polymerized herein are ethylene, a styrene and a norbornene. 
Norbornene and styrene may be present in the same polymerization, and a 
copolymer may be produced. By a styrene herein is meant a compound of the 
formula 
##STR9## 
wherein R.sup.26, R.sup.27, R.sup.26, R.sup.29 and R.sup.30 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.sup.26, R.sup.27, R.sup.26, R.sup.29 and 
R.sup.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 
##STR10## 
wherein "a" represents a single or double bond. 
Representative monomers are compounds (XXXV) and (XXXX) as follows: 
##STR11## 
wherein R.sup.46, R.sup.47, R.sup.48, and R.sup.49 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.sup.46 and 
R.sup.48 taken together can be part of carbocyclic ring (saturated, 
unsaturated or aromatic); or R.sup.46 and R.sup.47 and/or R.sup.48 and 
R.sup.45 taken together are an alkylidene group. In these structures "z" 
is 1 to 5. 
Examples of such norbornenes include norbornadiene, 2-norbornene, 
5-methyl-2-norbornene, 5-hexyl-2-norbornene, 5-ethylidene-2-norbornene, 
vinylnorbornene, dicyclopentadiene, dihydrodicyclopentadiene, 
tetracyclododecene, trimers of cyclopentadiene, halogenated norbornenes 
wherein R.sup.46, R.sup.47, R.sup.48 and R.sup.49 may also be halogen or 
fully halogenated alkyl groups such as C.sub.w F.sub.2w+1 wherein w is 1 
to 20, such as perfluoromethyl and perfluorodecyl. 
The halogenated norbornenes can be synthesized via the Diels-Alder reaction 
of cyclopentadiene an appropriate dieneophile, such as F.sub.3 
CC.ident.CCF.sub.3 or R.sup.49.sub.2 C=CR.sup.49 C.sub.w F.sub.2w+1 
wherein each R.sup.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 substituents 
include halo, ester, keto (oxo), amino, imino, carboxyl, phosphite, 
phosphonite, phosphine, phosphinite, thioether, amide, nitrile, and ether. 
Preferred substituents are halo, ester, amino, imino, carboxyl, phosphite, 
phosphonite, phosphine, phosphinite, thioether, and amide. By benzyl is 
meant the C.sub.6 H.sub.5 CH.sub.2 -- radical, and substituted benzyl is a 
radical in which one or more of the hydrogen atoms is replaced by a 
substituent group (which may include hydrocarbyl). By phenyl is meant the 
C.sub.6 H.sub.5 -- 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 ring(s). A 
monovalent aromatic moiety has one free valence, and herein is termed an 
aryl moiety. If there is more than one aromatic ring in the radical, the 
ring may be joined by covalent bonds (as in biphenyl) or may be fused (as 
in 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 
ring(s) may be substituted by hydrocarbyl groups or other substitutents 
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 listed 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 in situ, such as mixtures of 
nickel compounds in 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 ligands 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, reversibly or irreversibly, 
displaceable by (III),(V), or any one of (XVI) to (XIX), (XXXVI) and 
(XXXVII). Such readily displaceable ligands include .eta..sup.4 
-1,5-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(.eta..sup.4 -1,5-cyclooctadiene)nickel0!. 
By the compound HX is meant the acid of a noncoordinating monoanion, or the 
equivalent thereof, i.e., a combination of compounds that will generate 
this acid. Noncoordinating anions are well known to the artisan, see for 
instance W. Beck., et al., Chem. Rev., vol. 88, 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 
noncoordinating anions are described in these references, Beck at p. 1411, 
and Strauss at p. 932, Table III. Also useful in this process in 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.sub.4.sup.-, PF.sub.6.sup.-, and BAF 
{tetrakis3,5-bis(trifluoromethyl)phenyl!borate}, SbF.sup.-, and BAF is 
especially preferred. The acids of these anions are known, for instance 
HBF.sub.4 is commercially available, and HBAF can be made by the method 
described in M. Brookhart, et al., Organometallics, vol. 11, p. 3920-3922 
(1992). 
In all forms of (III) it is preferred that R.sup.9 and R.sup.43 are 
hydrogen. If R.sup.43 is alkyl, it is preferred that it is methyl. In all 
forms of (III), each R.sup.2 may be independently hydrogen, hydrocarbyl or 
substituted hydrocarbyl, and it is preferred that each R.sup.2 is 
hydrogen, benzyl, substituted benzyl, phenyl or substituted phenyl. 
In one preferred form of (III), n is 1 and Q is --NR.sup.2 R.sup.43. It is 
preferred that R.sup.2 is hydrogen and that Ar.sup.1 is 2,6-dialkylphenyl 
or amide, carboxy, or keto substituted phenyl. More preferably, Ar.sup.1 
is 2,6-diisopropylphenyl, 2-carbomoylphenyl, 2-carboxyphenyl, or 
2-benzoylphenyl. 
In another preferred form of (III), n is 2 and each Q is --NR.sup.2 
R.sup.43. In this instance it is more preferred that R.sup.2 is hydrogen, 
and/or Ar.sup.1 is o-phenylene or 1,8-naphthylene, and it is especially 
preferred that Ar.sup.1 is 1,8-naphthylene. 
In (III), when n is 1 and Q is --CR.sup.9 =NR.sup.3, it is preferred that 
R.sup.9 is hydrogen, and R.sup.3 is preferably 2,6-dialkylphenyl, or 
amide, ester, carboxyl, keto, or halo substituted phenyl. More preferably, 
R.sup.3 is 2,6-diisopropylphenyl, 2-carbomoylphenyl, 2-carbomethoxyphenyl, 
2-carboxyphenyl, 1-fluoren-9-onyl, 1-anthraquinolyl, or pentafluorophenyl. 
Ar.sup.1 is aryl, or halo, ester, amino, imino, carboxyl, phosphite, 
phosphonite, phosphine, phosphinite, ether, thioether, or amide 
substituted phenyl. More preferably, Ar.sup.1 is diphenylmethyl, 
9-anthracenyl, 2-furanyl, 2-thiofuranyl, 2-phenolyl, or 
2-hydroxy-naphthyl. When Ar.sup.1 is diphenylmethyl, these tautomeric 
forms are believed to exist when these compounds are complexed to nickel. 
When in (III) n is 2 and Q is --CR.sup.9 =NR.sup.3, it is preferred that 
Ar.sup.1 is p-phenylene, and that R.sup.3 is 2,6-disubstituted phenyl in 
which the substitutents are halo, alkyl, or halo and alkyl. 
In (III), when Q is --NHR.sup.2, R.sup.2 taken together with Ar.sup.1 may 
form a carbocyclic or heterocyclic ring, as long as the atom of R.sup.2 
attached directly to the nitrogen atom is a saturated carbon atom. Thus 
another preferred compound (III) is 
##STR12## 
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.sup.4, R.sup.5, R.sup.6, 
R.sup.7 and R.sup.10 are hydrogen, and both of R.sup.8 are 
2,6-dialkylphenyl, especially 2,6-diisopropylphenyl, or cyclohexyl. In 
another preferred compound (V) m is 1, all of R.sup.4, R.sup.5, R.sup.6, 
and R.sup.7 are hydrogen, both of R.sup.8 are phenyl, and both of R.sup.10 
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 olefin polymerization catalyst. 
In (XVI) is preferred that Ar.sup.2 is phenyl, 2-pyridyl, or 
3-hydroxyl-2-pyridyl, and/or R.sup.10 is hydrogen, phenyl, 
2,6-diisopropylphenyl,1-naphthyl, 2-methyl-1-naphthyl, or 2-phenylphenyl. 
In (XVII) it is preferred that R.sup.12 and R.sup.14 are hydrogen, and/or 
R.sup.13 is hydrogen or t-butyl, and/or R.sup.11 and R.sup.15 are both 
t-butyl or both phenyl, and/or R.sup.11 is t-butyl and R.sup.15 is 
2-hydroxy-3,5-di-t-butylphenyl. Note that when R.sup.15 is 
2-hydroxy-3,5-di-t-butylphenyl the compound contains 2 phenolic hydroxy 
groups, both of which are sterically hindered. 
The steric effect of various groupings has been quantified by a parameter 
called E.sub.s, see R. W. Taft, Jr., J. Am. Chem. Soc., vol. 74, p. 
3120-3128 (1952), and M. S. Newman, Steric Effects in Organic Chemistry, 
John Wiley & Sons, New York, 1956, p. 598-603. For the purposes herein, 
the E.sub.s values are those described in these publications. If the value 
for E.sub.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.sub.s value for the ortho (or other substituents closely 
adjacent to the --OH group) substitutents in the ring be about -1.5 or 
less, more preferably about -3.0 or less. Thus in a compound such as 
2,4,6-tri-t-butylphenol only the E.sub.s values for the 2 and 6 
substituted t-butyl groups would be applicable. 
In (XX) it is preferred that both R.sup.16 and R.sup.17 are hydrogen or 
that both are acyl. A preferred acyl group is CH.sub.3 C(O)--. 
In (XXI) it is preferred that Ar.sup.3 is phenyl or substituted phenyl, 
more preferably phenyl. 
In (XXII) it is preferred that both of R.sup.18 and R.sup.19 are methyl, or 
both are hydrogen. 
In (XXIII) it is preferred that Ar.sup.4 is phenyl or substituted phenyl, 
more preferably phenyl. 
In (XXIV) it is preferred that Ar.sup.5 and Ar.sup.6 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.sup.7 and Ar.sup.8 are independently 
phenyl or substituted phenyl. In a specific preferred compound, Ar.sup.7 
is phenyl, or p-tolyl and Ar.sup.8 is 2,6-diisopropylphenyl. 
In (XXVII) it is preferred that R.sup.25 is methyl. Specific preferred 
compounds are 
##STR13## 
Note that in one of these compounds there are 2 thiourea groups present. 
In (XXVIII) it is preferred that R.sup.22, R.sup.23 and R.sup.24 are each 
independently o-tolyl, 2,4,6-trimethoxyphenyl, 2,6-dimethoxyphenyl, 
2-methoxyphenyl, and 2,3,6-trimethoxyphenyl. Other preferred groups for 
R.sup.24 are ethyl, isopropyl and phenyl. It is also preferred that 
R.sup.24 is an aryl moiety. In another preferred form, when R.sup.22, 
R.sup.23 and/or R.sup.24 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 (XVIII) is 
1,3-bis(bis-2,6-dimethoxyphenyl)phosphino!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.sup.22, R.sup.23, and R.sup.24 (when it 
is an aryl moiety) contain electron donating groups bound to the aromatic 
moiety through a carbon atom of art 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 .sigma. constant. For ortho (adjacent) substituents one 
may use the Taft .sigma.* constant as determined by measurements on 
orthobenzoate 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 Chemistry, 2nd Ed., Cornell 
University Press, Ithaca, 1969, p. 1220-1226. It is preferred that the 
total of the .sigma. and .sigma.* constants for any of the groups 
R.sup.22, R.sup.23, and R.sup.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 
.sigma. and .sigma.* 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.sup.11 is 2,6-dialkylphenyl, more 
preferably 2,6-dimethylphenyl or 2,6-diisopropylphenyl It is preferred 
that R.sup.42 is --C(O)--NR.sup.41 --Ar.sup.11. It is preferred that 
R.sup.41 is hydrogen. 
In (XXXVII) it is preferred that m is 1, and/or all of R.sup.4, R.sup.5, 
R.sup.6 and R.sup.7 are hydrogen, and/or both of R.sup.8 are aryl 
moieties, more preferably both of R.sup.8 are 2,6-dialkylphenyl, and 
especially preferably both of R.sup.8 are 2,6-dimethylphenyl. 
In some of the compounds herein, the group --CHPh.sub.2, diphenylmethyl, 
may appear, especially when the methine 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.sub.2 (the imine form) or as --NH--CH=CPh.sub.2 (amine form). 
It has been found that in the free compounds (not complexed to nickel) 
this group is usually in the amine form. However, in a few of the nickel 
complexes of these types of compounds the preliminary evidence indicates 
the ligand is present in the imine 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 in the 
literature, and/or are available commercially or form laboratory supply 
houses, or are described in the Examples herein. 
The polymerization may also be carried out by L.sup.1.sub.q L.sup.2.sub.r 
L.sup.3.sub.s L.sup.4.sub.t Ni!.sup.+ X.sup.- (XXXIII), which may be 
formed in situ or added directly to the initial polymerization mixture. 
For example, (XXXIII) may be in the form of a .pi.-allyl complex. By a 
.pi.-allyl group is meant a monoanionic radical with 3 adjacent sp.sup.2 
carbon atoms bound to a metal center in an .eta..sup.3 fashion. The three 
sp.sup.2 carbon atoms may be substituted with other hydrocarbyl groups or 
functional groups. Typical .pi.-allyl groups include 
##STR14## 
wherein R is hydrocarbyl. In (XXXIII) when it is a .pi.-allyl type 
complex, L.sup.3 and L.sup.4 taken together are the .pi.-allyl group. As 
shown in many of the Examples herein, these .pi.-allyl compounds may be 
stable, and may be used themselves to initiate the olefin polymerization. 
Initiation with .pi.-allyl compounds may be sluggish at times. Initiation 
of .pi.-allyl compounds can be improved by using one or more of the 
following methods: 
Using a higher temperature such as about 80.degree. C. 
Decreasing the bulk of the ligand, such as R.sup.2 and R.sup.5 being 
2,6-dimethylphenyl instead of 2,6-diisopropylphenyl. 
Making the .pi.-allyl ligand more bulky, such as using 
##STR15## 
rather than the simple .pi.-allyl group itself. Having a Lewis acid 
present while using a functional .pi.-allyl. Relatively weak Lewis acids 
such a triphenylborane, tris(pentafluorophenyl)borane, and tris 
3,5-trifluoromethylphenyl)borane, are preferred. Suitable functional 
groups include chloro and ester. "Solid" acids such as montmorillonite may 
also be used. 
However, (XXXIII) may also be present in the polymerization in other 
"forms". For instance, L.sup.3 may be an olefin, such as ethylene, a 
norbornene or a styrene or a ligand capable of being displaced by an 
olefin. 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 nitriles such as acetonitrile. 
When L.sup.3 is an olefin, L.sup.4 may be --R.sup.35 R.sup.36. R.sup.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.sup.35. In this form (XXXIII) may be said to be a living ended polymer, 
further polymerization adding more repeat units to R.sup.35. R.sup.36 may 
be thought of as the end group of the polymeric group R.sup.35, and may be 
derived from the similar grouping such as R.sup.38 which was originally 
coordinated to the nickel. 
When L.sup.3 and L.sup.4 in (XXXIII) taken together are (XXXII), (XXXIII) 
may also be thought of as a living polymer. This type of grouping is often 
referred to as an "agostic" coordination, and in this group --R.sup.35 
R.sup.36 may be thought of in the same way as described above. Whether a 
living ended molecule will be in a form with a coordinated olefin or 
contain (XXXII) will depend on the other ligands coordinated to nickel, 
and the nature of the olefin 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.sup.1 and L.sup.2 may be a single neutral bidentate 
ligand of the same formula as when L.sup.1 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 in (XXXIII). 
This may depend on the ligand itself, what the ratio of ligand to Ni is, 
what the other ligands may be, and whether there are any other compounds 
present which may also act as ligands. 
When r in (XXXIII) is zero, simple dimers (containing 2 Ni atoms) with 
bridging ligands of the compound L.sup.1 L.sup.3 L.sup.4 Ni!.sup.+ 
X.sup.- are also included within the definition of (XXXIII). For instance 
a dimer containing L.sup.1, r is zero, and L.sup.3 and L.sup.4 are 
combined into an .pi.-allyl group could have the formula 
##STR16## 
In this structure both L.sup.1 ligands are bridging between the 2 nickel 
atoms. This type of dimer is familiar to those skilled in the art, and is 
believed to readily disassociate into "monomeric" nickel compounds on 
exposure to olefin. 
Some of the forms of (XXXIII) are relatively unstable, and are difficult to 
isolate as pure compounds. Nevertheless their presence can be demonstrated 
by various methods 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 .sup.1 H and .sup.13 
C NMR. Such detection of living ends is usually best done when R.sup.35 
contains relatively few repeat units. 
(XXXIII) may be made by methods described herein, especially in the 
Examples, or may actually be formed in 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 olefins. 
The preparation of one of the catalyst systems, when (II) is used, may be 
carried out in solution. By solution is meant that (II) and (III), (V), 
(XVI) to (XIX), (XXXVI) or (XXXVII), and (IV) are at least initially 
somewhat soluble in the solvent chosen. By somewhat soluble is 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 olefins 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 the polymer product, may 
become insoluble as the polymerization proceeds. Useful solvents include 
hydrocarbons such as toluene or benzene. Benzene is a preferred solvent. 
The benzene used herein is benzene-d.sub.6. 
Although it is not critical, when (II) is present it is preferred that the 
molar ratio of (III), (V), (XVI) to (XXVIII), (XXXVI) or (XXXVII):(II) is 
about 0.5 to 5, and the molar ratio of (IV):(II) is about 0.5 to about 10. 
It is also preferred that all the polymerizations be carried out at a 
temperature of about -100.degree. C. to about +200.degree. C., more 
preferably about -20.degree. C. to about +100.degree. C. 
The polymers produced by this process are useful as molding resins, films 
and elastomers. 
Most of the formulas 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 is 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. 
This may be illustrated 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: 
##STR17## 
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 method, 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 processes 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 (II) as a starting material than when using a preformed .pi.-allyl 
complex. 
Determining the activity of any particular compound which is described 
herein is relatively easy. The compound may be used in any of the 
polymerization systems described herein, and if needed the conditions, 
such as temperature and pressure, may be varied. Particularly for 
polymerizations in which the active nickel catalyst is formed in 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 to run and don't involve much experimentation. 
It is also noted that some forms of (XXXIII) may be prepared by other 
methods known in the art, see for instance copending U.S. application Ser. 
No. 08/590,650, filed Jan. 24, 1996 (CR9608D) which is hereby included by 
reference. 
In all of the polymerization processes and polymerization catalysts herein 
it is preferred that one or more of the following not be significantly 
present: an organoaluminum compound; an aluminum halide; any other 
transition metals, especially titanium and/or zirconium; reducing agents, 
especially metal or metalloid 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 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 Examples the following abbreviations are used: 
BAF-{tetrakis 3,5 -bis(trifluoromethyl)phenyl!borate} 
Bu-butyl 
COD-.eta..sup.4 -1,5-cyclooctadiene 
Cy-cyclohexyl 
DSC-differential scanning calorimetry 
Et-ethyl 
Me-methyl 
Ph-phenyl (C.sub.6 H.sub.5 --) 
RT-room temperature 
Tg-glass transition temperature 
THF-tetrahydrofuran 
TLC-thin layer chromatography 
Tm-melting point 
In the Examples, all ethylene pressures are gauge pressures unless 
otherwise noted. The formulas given for the nickel complexes of specific 
ligands in the Examples may not be accurate and are for illustration 
purposes only. They represent the best estimate of the structure (or one 
of several possible structures) based on available data.

EXAMPLE 1 
Under a nitrogen atmosphere, Ni(COD).sub.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.sub.2 O).sub.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 6.9MPa C.sub.2 H.sub.4 for 18 h at 25.degree. 
C. The final reaction mixture contained polyethylene, which was washed 
with methanol and dried; yield of polymer=9.1 g. .sup.1 H NMR (CDCl.sub.2 
CDCl.sub.2, 120.degree. C.) showed that this sample contained 90 
methyl-ended branches per 1000 methylenes. Two melting points were 
observed by differential scanning calorimetry: a very broad melting point 
centered at approximately 0.degree. C., and a sharp melting point at 
115.degree. C. 
##STR18## 
EXAMPLE 2 
Under a nitrogen atmosphere, Ni(COD).sub.2 (0.017 g, 0.06 mmol) and 
compound (VII) (0.023 g, 0.06 mmol) were dissolved in benzene (5.0 mL). To 
the resulting solution was added HBAF (Et.sub.2 O.sub.2).sub.2 (0.060 g, 
0.06 mmol). The resulting solution war 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 C.sub.2 H.sub.4 for 18 h at 
25.degree. C. The final reaction mixture contained polyethylene, which was 
filtered off, washed with methanol and dried; yield of polymer=4.9 g. By 
.sup.1 H NMR integration it was shown that this material was branched 
polyethylene containing 109 methyl-ended branches per 1000 methylenes. 
.sup.1 H NMR (CDCl.sub.3) d 1.24 (s, methylene and methine protons), 0.82 
(d, methyls). 
##STR19## 
EXAMPLE 3 
Under a nitrogen atmosphere, Ni(COD).sub.2 (0.017 g, 0.06 mmol) and 
compound (VIII) (0.024 g, 0.06 mmol) were dissolved in benzene (5.0 mL). 
To the resulting solution was added HBAF (Et.sub.2 O.sub.2).sub.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 C.sub.2 H.sub.4 for 18 h at 
25.degree. C. The final reaction mixture contained polyethylene, which was 
filtered off, washed with methanol and dried; yield of polymer=0.26 g. 
.sup.1 H NMR (C.sub.6 D.sub.3 Cl.sub.3, 120.degree. C.) showed that this 
sample contained 18 methyl-ended branches per 1000 methylenes. 
##STR20## 
EXAMPLE 4 
Under a nitrogen atmosphere, Ni(COD).sub.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.sub.2 O.sub.2).sub.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 C.sub.2 H.sub.4 for 18 h at 
25.degree. C. The final reaction mixture contained polyethylene, which was 
washed with methanol and dried; yield of polymer=0.73 g. T.sub.m 
=126.9.degree. C. (second heat) as determined by DSC. .sup.1 H NMR 
(CDCl.sub.2 CDCl.sub.2, 25.degree. C.) showed that this sample contained 
approximately 7 methyl-ended branches per 1000 methylenes. 
##STR21## 
EXAMPLE 5 
Under a nitrogen atmosphere, Ni(COD).sub.2 (0.017 g, 0.06 mmol) and 
compound (X) (0.030 g, 0.06 mmol) were dissolved in benzene (5.0 mL). To 
the resulting solution was added HBAF (Et.sub.2 O.sub.2).sub.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 C.sub.2 H.sub.4 for 18 h at 
25.degree. C. The final reaction mixture contained polyethylene, which was 
washed with methanol and dried; yield of polymer=1.40 g. T.sub.m 
=123.6.degree. C. as determined by DSC. .sup.1 H NMR (CDCl.sub.2 
CDCl.sub.2, 120.degree. C.) showed that this sample contained 
approximately 10 methyl-ended branches per 1000 methylenes. 
##STR22## 
EXAMPLE 6 
Under a nitrogen atmosphere, Ni(COD).sub.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.sub.2 O.sub.2).sub.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 C.sub.2 H.sub.4 for 18 h at 
25.degree. C. The final reaction mixture contained polyethylene, which was 
filtered off, washed with methanol and dried; yield of polymer=0.43 g. 
.sup.1 H NMR (CDCl.sub.2 CDCl.sub.2, 120.degree. C.) showed that this 
sample contained 19 methyl-ended branches per 1000 methylenes. 
##STR23## 
EXAMPLE 7 
Under a nitrogen atmosphere, Ni(COD).sub.2 (0.017 g, 0.06 mmol) and 
2,6-diisopropylaniline (0.011 g, 0.06 mmol) were dissolved in benzene (5.0 
mL). To the resulting solution was added HBAF (Et.sub.2 O.sub.2).sub.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 C.sub.2 
H.sub.4 for 18 h at 25.degree. C. The final reaction mixture contained 
polyethylene, which was filtered off, washed with methanol and dried; 
yield of polymer=0.72 g. T.sub.m =121.3.degree. C. (second heat) as 
determined by DSC. .sup.1 H NMR (C.sub.6 D.sub.3 Cl.sub.3, 120.degree. C.) 
showed that this sample contained 26 methyl-ended branches per 1000 
methylenes. Another experiment run under identical conditions afforded 
0.17 g of polymer; three other experiments 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, Ni(COD).sub.2 (0.017 g, 0.06 mmol) and 
2,6-diethylaniline (0.018 g, 0.12 mmol) were dissolved in benzene (5.0 
mL). To the resulting solution was added HBAF (Et.sub.2 O.sub.2).sub.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 C.sub.2 
H.sub.4 for 14 h at 25.degree. C. The final reaction mixture contained 
polyethylene, which was filtered off, washed with methanol and dried; 
yield of polymer=0.34 g. T.sub.m =122.5.degree. C. (second heat) as 
determined by DSC. 
EXAMPLE 9 
Under a nitrogen atmosphere, Ni(COD).sub.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.sub.2 O.sub.2).sub.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 C.sub.2 H.sub.4 for 14 h at 25.degree. 
C. The final reaction mixture contained polyethylene, which was filtered 
off, washed with methanol and dried; yield of polymer=0.049 g. T.sub.m 
=112.0.degree. C. as determined by differential scanning calorimetry. 
EXAMPLE 10 
Under a nitrogen atmosphere, Ni(COD).sub.2 (0.017 g, 0.06 mmol) and 
1,8-diaminonaphthalene (0.010 g, 0.06 mmol) Were dissolved in benzene (5.0 
mL). To the resulting solution was added HBAF (Et.sub.2 O.sub.2).sub.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 C.sub.2 
H.sub.4 for 18 h at 25.degree. 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.sub.m =37.0.degree. C. (second heat). 
EXAMPLE 11 
Under a nitrogen atmosphere, Ni(COD).sub.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.sub.2 O.sub.2).sub.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 C.sub.2 H.sub.4 for 18 h; 
during this time the temperature inside the reactor varied between 
25.degree. and 33.degree. C. The final reaction mixture contained 
polyethylene, which was filtered off, washed with methanol and dried; 
yield of polymer=0.13 g. T.sub.m =119.3.degree., 129.0.degree. C. as 
determined by DSC. 
##STR24## 
EXAMPLE 12 
Under a nitrogen atmosphere, Ni(COD).sub.2 (0.017 g, 0.06 mmol) and 
ortho-phenylenediamine (0.013 g, 0.12 mmol) were dissolved in benzene (5.0 
mL). To the resulting solution was added HBAF (Et.sub.2 O.sub.2).sub.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 C.sub.2 
H.sub.4 for 18 h at 25.degree. C. The final reaction mixture contained 
polyethylene, which was filtered off, washed with methanol and dried; 
yield of polymer=0.052 g. T.sub.m =98.0.degree., 119.0.degree. C. as 
determined by DSC. 
EXAMPLE 13 
Under a nitrogen atmosphere, Ni(COD).sub.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 (Et.sub.2 O.sub.2).sub.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 C.sub.2 H.sub.4 for 18 h at 
25.degree. C. The final reaction mixture contained polyethylene, which was 
filtered off, washed with methanol and dried; yield of polymer=0.76 g. 
##STR25## 
EXAMPLE 14 
Under a nitrogen atmosphere, Ni(COD).sub.2 (0.017 g, 0.06 mmol) and 
compound (XIV) (0.030 g, 0.06 mmol) were dissolved in benzene (5.0 mL). To 
the resulting solution was added HBAF (Et.sub.2 O.sub.2).sub.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 C.sub.2 H.sub.4 for 18 h; 
during this time the temperature inside the reactor varied between 
25.degree. and 33.degree. C. The final reaction mixture contained 
polyethylene, which was filtered off, washed with methanol and dried; 
yield of polymer=0.039 g. T.sub.m =126.2.degree. C. as determined by DSC. 
##STR26## 
EXAMPLE 15 
Under a nitrogen atmosphere, Ni(COD).sub.2 (0.017 g, 0.06 mmol) and 
anthranilic acid (0.008 g, 0.06 mmol) were dissolved in benzene (5.0 mL). 
To the resulting solution was added HBAF (Et.sub.2 O.sub.2).sub.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 C.sub.2 H.sub.4 for 18 h; 
during this time the temperature inside the reactor varied between 
25.degree. and 39.degree. C. The final reaction mixture contained 
polyethylene, which was filtered off, washed with methanol and dried; 
yield of polymer=1.74 g. T.sub.m =118.4.degree. C. as determined by DSC. 
EXAMPLE 16 
Under a nitrogen atmosphere, Ni(COD).sub.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.sub.2 O).sub.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 C.sub.2 H.sub.4 for 18 h; 
during this time the temperature inside the reactor varied between 
25.degree. and 34.degree. C. The final reaction mixture contained 
polyethylene, which was filtered off, washed with methanol and dried; 
yield of polymer=1.20 g. T.sub.m =120.2.degree., 132.3.degree. C. as 
determined by DSC. 
##STR27## 
EXAMPLE 17 
Synthesis of (VII) 
2,6-diisopropylaniline (17.7 g, 100 mmol), 1,2-dibromoethane (9.4 g, 50 
mmol), and diisopropylethylamine (20 mL) were heated to reflux for 2 days. 
Excess diisopropylethylamine was removed from the white crystals in vacuo, 
and the residue was washed with CH.sub.2 Cl.sub.2. The CH.sub.2 Cl.sub.2 
was evaporated to give a red-brown residue. The crude product was 
recrystallized from methanol to afford white crystals of (VII). 
EXAMPLE 18 
Synthesis of (IX) 
2,6-Diisopropylaniline (0.89 g, 5.0 mmol) and pentafluorobenzaldehyde (0.98 
g, 5.0 mmol) were dissolved in CH.sub.2 Cl.sub.2 (20 mL) and the reaction 
mixture was stirred overnight at room temperature. The solvent was removed 
in 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 
dissolved in anhydrous diethyl ether (15 mL) under nitrogen. To this 
stirred solution was slowly added the sodium salt of 
salicylaldehyde-2,6-dlisopropylanilineimine (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 was redissolved in 
approximately 3-4 mL petroleum ether. Slow evaporation of the solution at 
room temperature gave yellow crystals of (X). .sup.1 H NMR (CDCl.sub.3) d 
8.55 (s, 1H, N=CH), 8.25 (d, 1H, H.sub.aryl), 7.50-7.05 (mult, 15H, 
H.sub.aryl), 2.95 (sept, 2H, CMe.sub.2), 1.15 (d, 12H, CHMe.sub.2); 
.sup.31 P NMR (CDCl.sub.3) d 142.44. 
##STR28## 
The preparation of 1,1'-biphenyl-2,2'-diylphosphorochloridite can be found 
in the following references: WO 9303839, U.S. Pat. Nos. 4,769,498, and 
4,688,651, and Cuny, G. D., et al., J. Am. Chem. Soc. vol. 115, p. 2066 
(1993). 
Salicylaldehyde-2,6-diisopropylanilineimine was prepared by stirring an 
equimolar mixture of salicylaldehyde and 2,6-diisopropylaniline in the 
presence of a catalytic amount of formic acid in methanol for several days 
at room temperature; the product was from pentane at -78.degree. 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-dibenzc,e!1,2!oxaphosphorin and the sodium salt of 
salicylaldehyde-2,6-diisopropylanilineimine. .sup.1 H NMR (CDCl.sub.3) d 
8.20-7.00 (mult, 16H, N=CH and H.sub.aryl), 2.80 (sept, 2H, CHMe.sub.2), 
1.03 (overlapping d's,CHMe.sub.2, 12H); .sup.31 P NMR (CDCl.sub.3) d 128.8 
ppm. 
##STR29## 
6-Chloro-6H-dibenzc,e!1,2!oxaphosphorin was prepared according to a 
published procedure: Pastor, S. D., et al., Phosphorus and Sulfur vol. 31, 
p. 71 (1987). 
EXAMPLE 21 
Synthesis of (XIV) 
1,1'-biphenyl-2,2'-diylphosphorochloridite (0.125 g, 0.50 mmol) was 
dissolved in 15 mL 1,1 anhydrous ether/tetrahydrofuran under nitrogen. To 
this stirred solution was added the sodium salt of 
N-(ortho-hydroxy)benzyl-2,6diisopropylaniline (0.153 g, 0.50 mmol). 
Stirring was continued for another 5.5 hours before the solution was 
filtered. Evaporation of the filtrate afforded a nearly colorless oil. 
This material was redissolved in diethyl ether/petroleum ether (-1:2), and 
the solution cooled to -40.degree. C. A small amount of material 
precipitated from the solution and was removed. Slow evaporation of the 
solution afforded white crystals of compound XIV. .sup.1 H NMR 
(CDCl.sub.3) d 7.60-7.00 (mult, 15H, H.sub.aryl), 4.05 (s, 2H, CH.sub.2), 
3.40 ppm (br s, 1H, NH), 3.25 (sept, 2H, CHMe.sub.2); 1.10 (d, 12H, 
CHMe.sub.2). 
##STR30## 
N-(ortho-hydroxy)benzyl-2,6-diisopropylaniline sodium salt 
N-(ortho-hydroxy)benzyl-2,6-diisopropylaniline was prepared by NaBH.sub.4 
reduction of salicylaldehyde-2,6-diisopropylanilineimine in CH.sub.3 
OH/CHCl.sub.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-diisopropylphosphinoxy)benzyl-2,6-diisopropylanilineimine with 2 
equivalents of i-Bu.sub.2 AlH in toluene at 0.degree. C., followed by 
warming to room temperature and a basic workup. 
##STR31## 
N-(ortho-diisopropylphosphinoxy)benzyl-2,6-diisopropylanilineimine was 
prepared by reaction of salicylaldehyde-2,6-diisopropylanilineimine with 
chlorodiisopropylphosphine and triethylamine in toluene at room 
temperature. 
EXAMPLES 23-66 
These Examples were all done by the same general procedure. Under a 
nitrogen atmosphere, Ni(COD).sub.2 (0.017 g, 0.06 mmol) and the ligand to 
be tested (0.06 or 0.12 mmol) were dissolved in benzene (5.0 mL). To the 
resulting solution was added HBAF (Et.sub.2 O.sub.2).sub.2 (0.060 g, 0.06 
mmol). The resulting solution inside a 40 mL shaker tube glass insert was 
immediately frozen in a freezer inside the glove box. The glass insert was 
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 pressure for about 18 h. Any polyethylene in 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. The structures of 
the ligands (except if already shown above) are listed after Table 1. 
TABLE 1 
______________________________________ 
Ex. Ligan Ligand/ g PE Tm, .degree.C. 
______________________________________ 
23 50 1.0 24.4 123 
24 51 2.0 15.5 139 
25 52 1.0 11.0 -- 
26 53 2.0 10.2 124 
27 54 1.0 5.3 124 
28 55 2.0 4.6 125 
29 56 1.0 4.3 -- 
30 57 1.0 4.0 136 
31 58 1.0 3.9 118 
32 59 1.0 3.6 -- 
33 60 1.0 3.1 112 
34 61 1.0 3.0 124 
35 62 1.0 3.0 123 
36 63 1.0 2.9 128 
37 64 2.0 2.6 -- 
38 65 1.0 2.1 -- 
39 66 1.0 1.8 131 
40 67 1.0 1.7 118 
41 68 1.0 1.6 123 
42 69 1.0 1.5 -- 
43 70 1.0 1.5 -- 
44 (XIX) 1.0 1.4 121 
45 71 1.0 1.3 -- 
46 (XXV) 1.0 1.3 126 
47 72 1.0 1.1 131 
48 73 1.0 1.0 -- 
49 74 1.0 1.0 117 
50 75 1.0 .9 -- 
51 76 1.0 .9 -- 
52 77 1.0 .9 124 
53 78 1.0 .8 -- 
54 79 2.0 .8 -- 
55 80 2.0 .7 -- 
56 81 1.0 .7 127 
57 82 1.0 .7 65 
58 83 2.0 .6 -- 
59 (XVII 1.0 .6 -- 
60 84 1.0 .6 -- 
61 85 2.0 .6 -- 
62 86 2.0 .5 -- 
63 87 1.0 .5 -- 
64 88 1.0 .5 -- 
65 89 2.0 .5 -- 
66 90 1.0 .4 -- 
______________________________________ 
50 
##STR32## 
51 
##STR33## 
52 
##STR34## 
53 
##STR35## 
54 
##STR36## 
55 
##STR37## 
56 
##STR38## 
57 
##STR39## 
58 
##STR40## 
59 
##STR41## 
60 
##STR42## 
61 
##STR43## 
62 
##STR44## 
63 
##STR45## 
64 
##STR46## 
65 
##STR47## 
66 
##STR48## 
67 
##STR49## 
68 
##STR50## 
69 
##STR51## 
70 
##STR52## 
71 
##STR53## 
72 
##STR54## 
73 
##STR55## 
74 
##STR56## 
75 
##STR57## 
76 
##STR58## 
77 
##STR59## 
78 
##STR60## 
79 
##STR61## 
80 
##STR62## 
81 
##STR63## 
82 
##STR64## 
83 
##STR65## 
84 
##STR66## 
85 
##STR67## 
86 
##STR68## 
87 
##STR69## 
88 
##STR70## 
89 
##STR71## 
90 
##STR72## 
______________________________________ 
EXAMPLES 67-77 
Norbornene Polymerization 
General procedure: The reactions were carried out in a dry, deoxygenated 
atmosphere. The catalyst was weighed into a 20 ml glass scintillation vial 
and a stir bar was added. A solution of dry dichloromethane/norbornene (3 
ml, 43 mass % norbornene) was added and the resulting solutions stirred 
for 20-90 h. Each product was added to stirring methanol (in air) to 
precipitate the polymer. The polymer was filtered, washed with 
methanol/10% HCl solution and methanol and finally dried under vacuum. In 
each case purity was improved by redissolving the polymer in chloroform 
and reprecipitating with methanol. .sup.1 H-NMR (CDCl.sub.3) confirmed 
that the products were addition polymers of norbornene. Details and 
results of these polymerization are given in Table 2. Structures of the 
catalysts used are shown after Table 2 
TABLE 2 
______________________________________ 
Ex. Time, 
% 
No. Catalyst 
mmol h Yield Comments 
______________________________________ 
67 91 0.050 20 &gt;95% Solution was solidified 
within 5 min. 
68 92 0.041 20 &gt;95% Solidified over several h 
69 .sup. 93.sup.a 
0.030 20 93% Exothermic, boiled 
solvent 
70 94 0.016 44 45% Viscosity increased over 
several days 
71 .sup. 95.sup.a 
0.036 20 &gt;95% Exothermic, solidified 
within 1 min 
72 96 0.010 20 94% Solidified over 1 h 
73 98 0.039 20 85% No stirring after 20 min 
(too viscous) 
74 99 0.019 20 88% Exothermic, solid within 
10 sec 
75 100 0.020 20 81% Exothermic, solid within 
5 sec 
76 101 0.041 20 &gt;95% Solidified overnight 
77 102 0.018 20 87% Exothermic, solidified 
rapidly 
______________________________________ 
.sup.a End groups visible in .sup.1 H NMR of polymer indicate lower 
molecular weight 
91 
##STR73## 
92 
##STR74## 
93 
##STR75## 
94 
##STR76## 
95 
##STR77## 
95 
##STR78## 
96 
##STR79## 
98 
##STR80## 
99 
##STR81## 
100 
##STR82## 
101 
##STR83## 
102 
##STR84## 
______________________________________ 
EXAMPLES 78-85 
Styrene Polymerization 
General procedure: The reactions were carried out in a dry, deoxygenated 
atmosphere. The nickel containing catalyst was 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) was 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% HCl 
solution and methanol and finally dried under vacuum. Polymers were 
characterized using .sup.13 C-NMR (CDCl.sub.3) which indicated that in 
each case the product was enriched in racemic diad units relative to 
atactic polystyrene for measuring tacticities of polystyrenes see T. 
Kawamura, et al., Macromol. Rapid Commun., vol. 15, p. 479-486 (1994)!. 
Details of each polymerization and results are shown in Table 3. 
Structures of catalysts are shown after Table 2, above. 
TABLE 3 
______________________________________ 
Ex. % 
No. Catalyst mmol Yield Comments 
______________________________________ 
78 91 0.017 37% Golden solution 
79 92 0.016 &gt;95% Brown viscous solution 
80 93 0.015 80% Rapid reaction, viscous brown 
solution 
81 95 0.017 71% Rapid, orange solution turns 
brown, viscous 
82 96 0.006 6% Golden solution 
83 98 0.016 84% Boils solvent, dark red viscous 
solution 
84 101 0.016 5% Yellow solution 
85 102 0.027 73% Yellow solution, rapidly became 
viscous 
______________________________________ 
EXAMPLES 86-94 
Styrene/Norbornene Copolymerization 
General procedure: The reactions were carried out in a dry, deoxygenated 
atmosphere. The catalyst was weighed into a 20 ml glass scintillation vial 
and dry dichloromethane (1 ml) and a stir bar added. A solution of dry 
dichloromethane (2 ml), styrene (2 ml, Aldrich Chemical Co., 99+%, 
filtered through alumina, phenothiazine inhibitor added) and 1.5 g 
norbornene (Aldrich Chemical Co., 99%) was 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% HCl solution and methanol and finally dried under 
vacuum. 
.sup.1 H-NMR(CDCl.sub.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 polystyrene) confirms 
that the product is a copolymer see for instance A. Benaboura, et al., 
C.R. Acad. Sc. Paris, Ser. 2, vol. 301, p. 229 (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 catalysts are shown after Table 2, 
above. 
TABLE 4 
______________________________________ 
Polymer 
Ex mmol Yield Mol % 
No Catalyst 
catalyst 
(g) styrene 
Comments 
______________________________________ 
86 91 0.019 0.72 g 
&lt;5% Golden solution, sticky 
polymer 
87 92 0.015 1.49 g 
11.1% Brown solution, polymer 
precipitated 
88 93 0.012 2.47 g 
13.7% Exothermic, precipitated 
after 5 min 
89 95 0.019 2.62 g 
50.8% Orange solution turned 
red, precipitated 
90 97 0.013 0.28 g 
&lt;5% Brown solution, small 
amount polymer 
91 98 0.019 2.93 g 
41.4% Red solution, exothermic, 
precipitated 
92 99 0.009 2.64 g 
58.1% Exothermic, golden 
solution, precipitated 
93 100 0.015 2.15 g 
24.2% Gold solution, 
exothermic, precipitated 
94 101 0.023 1.54 g 
5.2% Yellow solution, polymer 
precipitated 
______________________________________ 
EXAMPLES 95-107 
Following the procedure of Examples 23-66, ethylene was polymerized. The 
results are reported in Table 5. The structures of the ligands are listed 
after Table 5. 
TABLE 5 
______________________________________ 
Ex. No. Ligand Ligand/Ni 
g PE 
______________________________________ 
95 102 1.0 13.8 
96 103 1.0 11.6 
97 104 1.0 10.8 
98 105 1.0 4.3 
99 106 1.0 1.8 
100 107 1.0 1.5 
101 108 1.0 1.4 
102 109 1.0 1.2 
103 110 1.0 0.9 
104 11 1.0 0.6 
105 112 1.0 0.4 
106 113 1.0 0.4 
107 114 1.0 0.2 
______________________________________ 
102 
##STR85## 
103 
##STR86## 
104 
##STR87## 
105 
##STR88## 
106 
##STR89## 
107 
##STR90## 
108 
##STR91## 
109 
##STR92## 
110 
##STR93## 
111 
##STR94## 
112 
##STR95## 
113 
##STR96## 
114 
##STR97## 
______________________________________ 
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 equiv of 
(allyl)Ni(m-X)!.sub.2 (X=Cl or Br) was dissolved in Et.sub.2 O. 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)!.sub.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 .sup.1 H and .sup.13 
C spectroscopic assignments of the BAF counterion in CD.sub.2 Cl.sub.2 
were invariant for different complexes and temperatures and are not 
repeated in the spectroscopic data for each of the cationic allyl 
complexes: 3,5-C.sub.6 H.sub.3 -(CF.sub.3).sub.2 !.sub.4.sup.- (BAF). 
.sup.1 H NMR (CD.sub.2 Cl.sub.2) d 7.74 (s, 8, H.sub.o), 7.57 (s, 4, 
H.sub.p); .sup.13 C NMR (CD.sub.2 Cl.sub.2) d 162.2 (q, J.sub.CB =37.4, 
C.sub.ipso), 135.2 (C.sub.o), 129.3 (q, J.sub.CF =31.3, C.sub.m), 125.0 
(q, J.sub.CF =272.5, CF.sub.3), 117.9 (C.sub.p). 
General Procedure for the Screening of Ethylene 
Polymerization by Nickel Allyl Initiators. In the drybox, a glass insert 
was loaded with the isolated allyl initiator synthesized by the above 
general procedure. The insert was cooled to -35.degree. C. in the drybox 
freezer, 5 mL of solvent (typically C.sub.6 D.sub.6 or CDCl.sub.3) was 
added to the cold insert, and the insert was then capped and sealed. 
Outside of the drybox, the cold tube was placed under 6.9 MPa of ethylene 
and allowed to warm to RT as it was shaken mechanically for approximately 
18 h. An aliquot of the solution was used to acquire a .sup.1 H NMR 
spectrum. The remaining portion was added to .about.20 mL of MeOH in order 
to precipitate the polymer. The polyethylene was isolated and dried under 
vacuum. 
EXAMPLE 108 
##STR98## 
The general synthesis of nickel allyl initiators was followed using 64 mg 
of ligand, 53 mg of (C.sub.3 H.sub.5)Ni(.mu.-Cl)!.sub.2, and 347 mg of 
NaBAF. A wheat yellow powder (307 mg) was isolated. .sup.1 H and .sup.13 C 
NMR spectra are consistent with the above structure with one equiv of 
Et.sub.2 O present. In particular, at -80.degree. C. two sets of amino 
proton resonances are observed and are coupled to each other. This is 
consistent with the above structure in which both nitrogen atoms are bound 
to nickel. At room temperature (20.degree. C.), one broad resonance is 
observed at 5.64 ppm for all of the amino protons: .sup.1 H NMR (CD.sub.2 
Cl.sub.2, 300 MHz, -80.degree. C.) d 7.81 (d, 2, J=8.09, H.sub.o or 
H.sub.p), 7.41 (t, 2, J=8.1, H.sub.m), 7.26 (d, 2, J=6.74, H.sub.o or 
H.sub.p), 5.49 (m, 1, J=6.7, H.sub.2 CCHCH.sub.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, O(CH.sub.2 
CH.sub.3).sub.2), 3.26 (d, 2, J=6.8 (HH'CCHCHH'), 2.17 (d, 2, J=13.5, 
HH'CCHCHH'), 0.92 (t, 6, J=6.1, O(CH.sub.2 CH.sub.3).sub.2); .sup.13 C NMR 
(CD.sub.2 Cl.sub.2, 75 MHz, rt) d 136.1, 130.4, 129.0, 126.7, 123.2 and 
121.7 (C.sub.aryl), 115.4 (H.sub.2 CCHCH.sub.2), 65.9 (H.sub.2 
CCHCH.sub.2), 55.7 (O(CH.sub.2 CH.sub.3).sub.2), 14.9 (O(CH.sub.2 
CH.sub.3).sub.2. 
EXAMPLE 109 
The allyl initiator of Example 108 was used to polymerize ethylene in 
CDCl.sub.3 at RT according to the general polymerization procedure using 
24 mg of catalyst. Polyethylene was isolated (304 mg). 
EXAMPLE 110 
##STR99## 
The general synthesis of nickel allyl initiators was followed using 151 mg 
of ligand, 205 mg of (H2CCHCHPh)Ni(.mu.-Cl)!.sub.2, and 860 mg of NaBAF. 
A yellow-brown powder (694 mg) was isolated. The .sup.1 H NMR spectrum 
indicates that one equiv of Et.sub.2 O is present. The spectrum, 
particularly the observation of 4 inequivalent coupled amino protons, is 
consistent with the above structure in which both nitrogen atoms are bound 
to nickel. The amino resonances remain inequivalent at least up to 
60.degree. C.: .sup.1 H NMR (CD.sub.2 Cl.sub.2, 300 MHz, -40.degree. C.) d 
7.85-7.25 (m, 10, H.sub.aryl), 6.47 (d, 1, J=6.8, H.sub.aryl), 6.03 (t of 
d, 1, J=12.8, 7.2, H.sub.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.sub.2 
CHCHPh), 3.66 (d, 1, J=10.8, N'HH'), 3.41 (q, 4, J=7.2, O(CH.sub.2 
CH.sub.3).sub.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, O(CH.sub.2 CH.sub.3).sub.2). 
EXAMPLE 111 
The allyl initiator of Example 1110 was used to polymerize ethylene in 
C.sub.6 D.sub.6 at 80.degree. C. according to the general polymerization 
procedure using 67 mg of catalyst. No polyethylene was isolated under 
these conditions. However, the .sup.1 H NMR spectrum of the reaction 
mixture indicated that butenes and higher olefins were produced in 
significant amounts. 
EXAMPLE 1112 
##STR100## 
The general synthesis of nickel allyl initiators was followed using 202 mg 
of ligand, 127 mg of (C.sub.3 H.sub.5)Ni(.mu.-Cl)!.sub.2, and 829 mg of 
NaBAF. A yellow-orange powder (967 mg) was isolated. The NMR spectra are 
consistent with the structure shown above, in which both nitrogen atoms 
coordinate to nickel. .sup.1 H NMR (CD.sub.2 Cl.sub.2, 300 MHz, rt) d 7.83 
(d of d, 2, J=5.9, 3.3, H.sub.m), 7.56 (s, 2, H.sub.o or H.sub.p), 7.54 
(d, 2, J=2.9, H.sub.o or H.sub.p), 6.10 (t of t, 1, J=13.4, 7.1, H.sub.2 
CCHCH.sub.2), 3.23 (d, 2, J=7.3, HH'CCHCHH'), 3.1 (br, 12, 
2.times.NMe.sub.2), 2.58 (d, 2, J=13.2, HH'CCHCHH'); .sup.13 C NMR 
(CD.sub.2 Cl.sub.2, 75 MHz, rt, nonaromatic carbons only) d 117.6 (H.sub.2 
CCHCH.sub.2), 60.2 (H.sub.2 CCHCH.sub.2), 55.1 (br, NMe.sub.2). 
EXAMPLE 113 
The allyl initiator of Example 112 was used to polymerize ethylene in 
CDCl.sub.3 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 was not isolated. The 1H NMR spectrum showed the production 
of butenes and a small amount of higher olefins. 
EXAMPLE 114 
##STR101## 
The general synthesis of nickel allyl initiators was followed using 103 mg 
of ligand, 100 mg of (H.sub.2 CCHCMe.sub.2)Ni(.mu.-Br)!.sub.2, and 427 mg 
of NaBAF. A pale pink powder (517 mg) was isolated. The NMR spectrum is 
consistent with the structure shown above, in which both nitrogen atoms 
coordinate to nickel. .sup.1 H NMR (CD.sub.2 Cl.sub.2, 300 MHz, rt) d 
8.2-7.4 (m, 6, H.sub.aryl), 5.33 (dd, 1, J=12.8, 7.4, H.sub.2 
CCHCMe.sub.2), 3.35-2.80 (br, 12, NMeMe', N'MeMe'), 2.78 (dd, 1, J=8.1, 
2.7, HH'CHCMe.sub.2), 1.75 (dd, 1, J=13.5, 2.7, HH'CHCMe.sub.2), 1.22 and 
0.73 (s, 3 each, H.sub.2 CCHCMeMe'). 
EXAMPLE 115 
The allyl initiator of Example 114 was used to polymerize ethylene in 
CDCl.sub.3 at RT according to the general polymerization procedure using 
66 mg of catalyst. Polyethylene was isolated (23 mg). 
EXAMPLE 116 
The allyl initiator of Example 114 was used to polymerize ethylene in 
CDCl.sub.3 at 80.degree. C. according to the general polymerization 
procedure using 62 mg of catalyst. No polyethylene was isolated; however, 
the .sup.1 H NMR spectrum of the reaction mixture showed the production of 
butenes, higher olefins, and a broad (CH.sub.2).sub.n peak at 1.25 ppm. 
EXAMPLE 117 
##STR102## 
The general synthesis of nickel allyl initiators was followed using 135 mg 
of ligand, 48 mg of (C.sub.3 H.sub.5)Ni(.mu.-Cl)!.sub.2, and 307 mg of 
NaBAF. A yellow powder (394 mg) was isolated. The .sup.1 H and .sup.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 in lesser 
amounts: .sup.1 H NMR (CD.sub.2 Cl.sub.2, 300 MHz, -40.degree. C.) d 
7.4-7.0 (m, 6, H.sub.aryl), 5.68 (m, 1, H.sub.2 CCHCH.sub.2), 5.53, 5.38, 
4.84 and 4.22 (m, 1 each, NCHH'C'HH'N'), 3.4-2.8 (m, 6, NH, N'H, 
CHMe.sub.2, C'HMe.sub.2, C"HMe.sub.2, C'"HMe.sub.2), 2.73 (d, 1, J=6.7, 
HH'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'HMeMe', C"HMeMe', C'"HMeMe'); .sup.13 C NMR (CD.sub.2 Cl.sub.2, 75 MHz, 
rt) d 140.9, 140.8, 139.9, 139.4, 138.9 and 138.4 (Ar: C.sub.ipso, 
C.sub.o, C.sub.o ' and Ar': C.sub.ipso, C.sub.o, C.sub.o '), 129.0, 128.8, 
127.1, 127.0, 125.4 and 125.1 (Ar: C.sub.m, C.sub.m ', C.sub.p and Ar': 
C.sub.m, C.sub.m ', C.sub.p), 116.1 (H.sub.2 CCHCH.sub.2), 60.7, 55.9, 
54.3 and 53.0 (H.sub.2 CCHC'H.sub.2, NCH.sub.2 C'H.sub.2 N'), 31.7, 30.5, 
30.0 and 29.4 (CHMe.sub.2, C'HMe.sub.2, C"HMe.sub.2, C'"HMe.sub.2), 26.4, 
26.0, 24.4, 24.2, 24.2, 24.2, 24.0 and 22.9 (CHMeMe', C'HMeMe', C"HMeMe', 
C'"HMeMe'). 
EXAMPLE 118 
The allyl initiator of Example 117 was used to polymerize ethylene in 
C.sub.6 D.sub.6 at 80.degree. C. according to the general polymerization 
procedure using 63 mg of catalyst. Polyethylene (3.49 g) was isolated. 
.sup.1 H NMR spectrum of the isolated polymer indicates the formation of 
branched polyethylene with roughly 100 methyl branches per 1000 carbon 
atoms. 
EXAMPLE 119 
The allyl initiator of Example 117 was used to polymerize ethylene in 
CDCl.sub.3 at 80.degree. C. according to the general polymerization 
procedure using 68 mg of catalyst. Polyethylene (1.69 g) was isolated. 
EXAMPLE 120 
##STR103## 
The general synthesis of nickel allyl initiators was followed using 106 mg 
of ligand, 53 mg of (C.sub.3 H.sub.5)Ni(.mu.-Cl)!.sub.2, and 349 mg of 
NaBAF. A yellow powder (394 mg) was isolated. The .sup.1 H and .sup.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 in lesser 
amounts: .sup.1 H NMR (CD.sub.2 Cl.sub.2, 300 MHz, rt) d 8.3-7.2 (m, 10, 
H.sub.aryl), 5.9 (m, 1, H.sub.2 CCHCH.sub.2), 3.9-2.8 (m, 10, HH'CCHCHH', 
NCH.sub.2 CH.sub.2 N', NCH.sub.2 CH.sub.3, N'CH.sub.2 CH.sub.3), 2.49 (d, 
1, J=13.6, HH'CCHCHH'), 2.15 (d, 1, J=13.6, HH'CCHCHH'), 1.36 end 1.17 (t, 
3 each, J=7.2, NCH.sub.2 CH.sub.3 and N'CH.sub.2 CH.sub.3); .sup.13 C NMR 
(CD.sub.2 Cl.sub.2, 75 MHz, rt) d 150.1 and 147.5 (Ph: C.sub.ipso and Ph': 
C.sub.ipso), 130.8, 130.8, 130.8, 130.7, 129.2, 128.9, 128.2, 124.0, 123.9 
and 122.6 (Ph: C.sub.o, C.sub.o ', C.sub.m, C.sub.m ' and C.sub.p ; Ph': 
C.sub.o, C.sub.o ', C.sub.m, C.sub.m ' and C.sub.p), 115.6 (H.sub.2 
CCHCH.sub.2), 59.6, 58.7, 58.3, 57.9, 57.3 and 56.4 (H.sub.2 CCHCH.sub.2, 
NCH.sub.2 CH.sub.3, N'CH.sub.2 CH.sub.3, NCH.sub.2 CH.sub.2 N'), 12.6 and 
11.8 (NCH.sub.2 CH.sub.3 and N'CH.sub.2 CH.sub.3). 
EXAMPLE 121 
The allyl initiator of Example 120 was used to polymerize ethylene in 
CDCl.sub.3 at 60.degree. C. according to the general polymerization 
procedure using 25 mg of catalyst. A few mg's of soft white polyethylene 
was isolated; the .sup.1 H NMR spectrum of this product shows branched 
polyethylene peaks at 1.25 ppm (CH.sub.2) and 0.85 ppm (CH.sub.3). 
EXAMPLE 122 
##STR104## 
The general synthesis of nickel allyl initiators was followed using 95 mg 
of ligand, 34 mg of (C.sub.3 H.sub.5)Ni(.mu.-Cl)!.sub.2, and 218 mg of 
NaBAF. A yellow powder (231 mg) was isolated. The .sup.1 H NMR spectrum is 
complex with more than one isomer apparently present. 
EXAMPLE 123 
The allyl initiator of Example 122 was used to polymerize ethylene in 
CDCl.sub.3 at 60.degree. C. according to the general polymerization 
procedure using 22 mg of catalyst. A few mg's of polyethylene was 
isolated; the .sup.1 H NMR spectrum of this product shows a --(CH.sub.2)-- 
peak at 1.2 ppm. The .sup.1 H NMR spectrum of the reaction mixture shows 
the production of butenes; branched polyethylene peaks are also observable 
at 1.25 ppm (CH.sub.2) and 0.85 ppm (CH.sub.3). 
EXAMPLE 124 
##STR105## 
The general synthesis of nickel allyl initiators was followed using 213 mg 
of ligand, 54 mg of (C.sub.3 H.sub.5)Ni(.mu.-Cl)!.sub.2, and 354 mg of 
NaBAF. An orange powder (391 mg) was isolated. Variable-temperature .sup.1 
H NMR and .sup.13 C NMR spectra are consistent with the above structure in 
which one methoxy group and the phosphorus atom are coordinated to nickel. 
.sup.1 H NMR spectral data are reported at both -100.degree. C. and 
20.degree. C. Four resonances for the allyl syn and anti protons are 
observed at -100.degree. C., while two resonances are observed at RT for 
these protons. The observation of the four syn and anti protons at 
-100.degree. C. supports probable coordination of the methoxy group to 
nickel: .sup.1 N NMR (CD.sub.2 Cl.sub.2, 300 MHz, -100.degree. C.) d 6.05 
(d, 6, J.sub.HP =4.1, C.sub.m), 5.59 (m, 1, H.sub.2 CCHCH.sub.2), 3.89 (d, 
I, J=6.75, HH'CHC'HH'), 3.76 (s, p-OMe), 3.67 (s, o-OMe), 3.07 (br s, 1, 
HH'CHC'HH'), 2.93 (dd, 1, J=13.5, 5.4, HH'CHCHH'), 1.74 (d, 1, J=12.1, 
HH'CCHCHH'); .sup.1 H NMR (CD.sub.2 Cl.sub.2, 300 MHz, 20.degree. C.) d 
6.13 (d, 6, J.sub.HP =b 2.7, C.sub.m), 5.62 (m, 1, H.sub.2 CCHCH.sub.2), 
3.81 (s, 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'); .sup.13 C NMR (CD.sub.2 Cl.sub.2, 75 MHz, rt) d 
164.0 (C.sub.p), 162.4 (d, J.sub.CP =4.9, C.sub.o), 113.7 (H.sub.2 
CCHCH.sub.2), 97.8 (d, J.sub.CP =60.4, C.sub.ipso to P), 91.1 (d, J=4.9, 
C.sub.m), 57.8 (H.sub.2 CCHCH.sub.2 and o-OMe, overlapping), 55.4 (p-OMe). 
EXAMPLE 125 
The allyl initiator of Example 124 was used to polymerize ethylene in 
CDCl.sub.3 at RT according to the general polymerization procedure using 
28 mg of catalyst. Butones were formed according to .sup.1 H NMR 
spectroscopy. 
EXAMPLE 126 
The allyl initiator of Example 124 was used to polymerize ethylene in 
C.sub.6 D.sub.6 at RT according to the general polymerization procedure 
using 28 mg of catalyst. Butones and some higher olefins were formed 
according to .sup.1 H NMR spectroscopy. 
EXAMPLE 127 
##STR106## 
The general synthesis of nickel allyl initiators was followed using 501 mg 
of ligand, 224 mg of (H.sub.2 C(CO.sub.2 Me)CH.sub.2)Ni(.mu.-Br)!.sub.2, 
and 834 mg of NaBAF. A yellow-green powder (391 mg) was isolated. .sup.1 H 
NMR spectrum of product is complex; the structure shown above is 
tentatively assigned by analogy to the parent (C.sub.3 H.sub.5) allyl 
complex. 
EXAMPLE 128 
The allyl initiator of Example 127 was used to polymerize ethylene in 
C.sub.6 D.sub.6 at RT according to the general polymerization procedure 
using 93 mg (0.06 mmol) of catalyst and 2 equiv (29 mg) of BPh.sub.3 
cocatalyst. Polyethylene (177 mg) was isolated. 
EXAMPLE 129 
The allyl initiator of Example 127 was used to polymerize ethylene in 
CDCl.sub.3 at RT according to the general polymerization procedure using 
93 mg (0.06 mmol) of catalyst and 2 equiv (61 mg) of B(C.sub.6 
F.sub.3).sub.3 cocatalyst. Polyethylene (90 mg) was isolated. 
EXAMPLE 130 
##STR107## 
The general synthesis of nickel allyl initiators was followed using 45 mg 
of ligand, 50 mg of (C.sub.3 H.sub.5)Ni(.mu.-Cl)!.sub.2, and 328 mg of 
NaBAF. A yellow powder (334 mg) was isolated. The .sup.1 H NMR spectral 
data is consistent with the structure shown above: .sup.1 H NMR (CD.sub.2 
Cl.sub.2, 300 MHz, rt) d 8.46 (d, 1, J=5.4, H.sub.aryl), 8.17 (t, 1, 
J=8.1, H.sub.aryl), 7.84 (d, 1, J=8.1, H.sub.aryl), 7.74 (m, 1, 
H.sub.aryl, overlaps with BAF: H.sub.o), 7.10 and 6.82 (br s, 1 each 
NHH'), 5.99 (m, 1, H.sub.2 CCHCH.sub.2), 3.57 (d, 2, J=6.8, HH'CCHCHH'), 
2.66 (d, 2, J=13.5, HH'CCHCHH'). .sup.13 C NMR (CD.sub.2 Cl.sub.2, 75 MHz, 
rt) d 173.5 (C=O), 146.4 (Caryl: C-C(O)NH.sub.2), 153.7, 141.4, 131.6 and 
123.9 (C.sub.aryl attached to hydrogen), 117.2 (H.sub.2 CCHCH.sub.2), 
(H.sub.2 CCHCH.sub.2 overlaps with CD.sub.2 Cl.sub.2 resonance). 
EXAMPLE 131 
The allyl initiator of Example 130 was used to polymerize ethylene in 
CDCl.sub.3 at RT according to the general polymerization procedure using 
63 mg of catalyst. A few mg's of polyethylene was isolated. According to 
the .sup.1 H NMR spectrum of the reaction mixture, significant amounts of 
butenes and higher olefins were produced. Polyethylene --CH.sub.2 -- 
resonance is identifiable at 1.25 ppm. 
EXAMPLE 132 
The allyl initiator of Example 130 was used to polymerize ethylene in 
C.sub.6 D.sub.6 at 80.degree. C. according to the general polymerization 
procedure using 64 mg of catalyst. Polyethylene (247 mg) was isolated. 
According to the .sup.1 H NMR spectrum of the reaction mixture, the 
reaction was productive in the formation of butenes and higher olefins. 
EXAMPLE 133 
##STR108## 
The general synthesis of nickel allyl initiators was followed using 52 mg 
of ligand, 50 mg of (C.sub.3 H.sub.5)Ni(.mu.-Cl)!.sub.2, and 328 mg of 
NaBAF. A yellow powder (328 mg) was isolated. The .sup.1 H NMR spectral 
data is consistent with the structure shown above: .sup.1 H NMR (CD.sub.2 
Cl.sub.2, 300 MHz, rt) d 11.34 (br s, 1, OH), 8.54 (br s, 1, NHH'), 7.99 
(d, 1, H=4.0, H.sub.aryl), 7.64 (d, 1, J=8.1, H.sub.aryl), 7.55 (t, 1, 
J=4.7, H.sub.aryl), 6.76 (br s, 1, NHH'), 5.5 (m, 1, HH'CCHCHH'), 3.40 
(br, HH'CCHCHH', 2.58 (br, HH'CCHCHH'). .sup.13 C NMR (CD.sub.2 Cl.sub.2, 
75 MHz, rt, assignments aided by an APT spectrum) .delta. 173.7 (CO), 
155.9 and 133.8 (C.sub.aryl not attached to hydrogen), 145.8, 132.3 and 
129.3 (C.sub.aryl attached to hydrogen), 116.6 (H.sub.2 CCHCH.sub.2), 
(H.sub.2 CCHCH.sub.2 resonances not observed neither overlapping with 
CD.sub.2 Cl.sub.2 resonance or broad and in the baseline). 
EXAMPLE 134 
The allyl initiator of Example 133 was used to polymerize ethylene in 
CDCl.sub.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 in 
C.sub.6 D.sub.6 at 80.degree. C. according to the general polymerization 
procedure using 60 mg of catalyst. Polyethylene (783 mg) was isolated. 
According to the .sup.1 H NMR spectrum of the reaction mixture, 
significant amounts of butenes and higher olefins were produced. 
EXAMPLE 136 
##STR109## 
The general synthesis of nickel allyl initiators was followed using 57 mg 
of ligand, 50 mg of (C.sub.3 H.sub.5)Ni(.mu.-Cl)!.sub.2, and 328 mg of 
NaBAF. A yellow powder (264 mg) was isolated. The .sup.1 H, .sup.13 C, and 
APT NMR spectral data is consistent with the structure shown above: .sup.1 
H NMR (CD.sub.2 Cl.sub.2, 300 MHz, rt) d 14.0 (br s, 1, OH), 8.10 (d, 1, 
J=8.1, H.sub.aryl), 7.65 (t, 1, J=8.1, H.sub.aryl), 7.47 (t, 1, J=8.1, 
H.sub.aryl), 7.21 (d, 1, J=8.1, H.sub.aryl), 5.83 (m, 1, H.sub.2 
CCHCH.sub.2), 4.34 (br s, 2, NH.sub.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 
CDCl.sub.3 at RT according to the general polymerization procedure using 
63 mg of catalyst. Polyethylene was not isolated. According to the .sup.1 
H NMR spectrum of the reaction mixture, significant amounts of butenes and 
higher olefins were produced. 
EXAMPLE 138 
##STR110## 
The general synthesis of nickel allyl initiators was followed using 83 mg 
of ligand, 50 mg of (C.sub.3 H.sub.5)Ni(.mu.-Cl)!.sub.2, and 328 mg of 
NaBAF. A red powder (381 mg) was isolated. .sup.1 H NMR (CD.sub.2 
Cl.sub.2, 300 MHz, rt): The complex formed a clear red solution in 
CD.sub.2 Cl.sub.2 with no precipitate present. However, the lock signal 
and spectrum were both broad, possibly indicating paramagnetism. The above 
structure is tentatively assigned by analogy to diamagnetic complexes 
containing ligands with similar donor fuctionality. 
EXAMPLE 139 
The allyl initiator of Example 138 was used to polymerize ethylene in 
CDCl.sub.3 at RT according to the general polymerization procedure using 
63 mg of catalyst. Polyethylene (88 mg) was isolated. 
EXAMPLE 140 
The allyl initiator of Example 138 was used to polymerize ethylene in 
C.sub.6 D.sub.6 at 80.degree. C. according to the general polymerization 
procedure using 60 mg of catalyst. Polyethylene (64 mg) was isolated. 
According to the .sup.1 H NMR spectrum of the reaction mixture, 
significant amounts of butenes and higher olefins were produced. 
EXAMPLE 141 
##STR111## 
The general synthesis of nickel allyl initiators was followed using 135 mg 
of ligand, 50 mg of (C.sub.3 H.sub.5)Ni(.mu.-Cl)!.sub.2, and 328 mg of 
NaBAF. An orange powder (403 mg) was isolated. The .sup.1 H, .sup.13 C, 
and APT NMR spectral data for the major product follows and is consistent 
with one isomer of the above structure. Other isomers may be present in 
lesser amounts: .sup.1 H NMR (CD.sub.2 Cl.sub.2, 300 MHz, rt) d 9.77 and 
8.83 (s, 1 each, N=CH and H.sub.aryl), 9.0-7.5 (m, 8, H.sub.aryl), 6.91 
and 6.63 (br s, 1 each, NHH'), 4.6 (br s, 1, H.sub.2 CCHCH.sub.2), 3.5-2.3 
(broad resonances in the baseline, HH'CCHCCHH'). .sup.13 C NMR (CD.sub.2 
Cl.sub.2, 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.sub.aryl not 
attached to hydrogen), 136.8, 133.7, 130.3, 130.2, 129.5, 129.3, 127.0, 
123.3 and 122.7 (C.sub.aryl attached to hydrogen), 113.8 (H.sub.2 
CCHCH.sub.2), (H.sub.2 CCHCH.sub.2 resonances were not observed neither 
overlapping with CD.sub.2 Cl.sub.2 resonance or broad and in the 
baseline). 
EXAMPLE 142 
The allyl initiator of Example 141 was used to polymerize ethylene in 
CDCl.sub.3 at RT according to the general polymerization procedure using 
68 mg of catalyst. Polyethylene (1.60 g) was isolated as a wax. 
EXAMPLE 143 
The allyl initiator of Example 141 was used to polymerize ethylene in 
C.sub.6 D.sub.6 at 80.degree. C. according to the general polymerization 
procedure using 60 mg of catalyst. Polyethylene (5.64 g) was isolated as a 
wax. 
EXAMPLE 144 
##STR112## 
The general synthesis of nickel allyl initiators was followed using 123 mg 
of ligand, 50 mg of (C.sub.3 H.sub.5)Ni(.mu.-Cl)!.sub.2, and 328 mg of 
NaBAF. A yellow powder (383 mg) was isolated. The .sup.1 H NMR spectrum is 
consistent with the above structure, although contamination by free ligand 
is indicated: .sup.1 H NMR (CD.sub.2 Cl.sub.2, 300 MHz, rt, i-Pr and allyl 
resonances only) d 5.97 (m, 1, H.sub.2 CCHCH.sub.2), 3.76 (br septet and 
br d, 1 each, CHMe.sub.2 and HH'CHCHH'), 3.53 (br d, 1, J.about.5.5, 
HH'CCHCHH'), 3.35 (br septet, 1, C'HMe.sub.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, CHMeMe' and C'HMeMe'). 
EXAMPLE 145 
The allyl initiator of Example was 144 used to polymerize ethylene in 
CDCl.sub.3 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 .sup.1 H NMR spectrum of the reaction mixture, 
significant amounts of hutches and higher olefins 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 in 
C.sub.6 D.sub.6 at 80.degree. C. according to the general polymerization 
procedure using 64 mg of catalyst. Polyethylene (96 mg) was isolated as a 
white powder. The .sup.1 H NMR spectrum shows the production of butenes 
and higher olefins. Polyethylene --CH.sub.2 -- resonance is identifiable 
at 1.25 ppm. 
EXAMPLE 147 
##STR113## 
The general synthesis of nickel allyl initiators was followed using 532 mg 
of ligand, 229 mg of (C.sub.3 H.sub.5)Ni(.mu.-Cl)!.sub.2, and 1.50 of 
NaBAF. 1.85 g of a yellow powder was isolated. Although the free ligand 
exists as the amine, the .sup.1 H and .sup.13 C NMR spectra are consistent 
with the ligand binding to the molecule as the imine: .sup.1 H NMR 
(THF-d.sub.8, 300 MHz, rt) d 8.75 (br s, 2, NH.sub.2), 8.55 (d, 1, J=5.4, 
N=CH), 7.9-7.0 (m, 14, H.sub.aryl), 5.56 (d, 1, J=5.4, CHPh.sub.2), 5.52 
(m, 1, H.sub.2 CCHCH.sub.2), 3.01 (d, 2, J=6.7, HH'CCHCHH'), 2.01 (d, 2, 
J=13.5, HH'CCHCH'); .sup.13 C NMR (THF-d.sub.8, 75 MHz, rt, non-aromatic 
carbons only, assignments aided by APT spectrum) d 181.7 (N=CH), 172.8 
(C=O), 113.8 (H.sub.2 CCHCH2), 58.7 (CHPh.sub.2), 54.5 (H.sub.2 
CCHCH.sub.2). 
EXAMPLE 148 
The allyl initiator of Example 147 was used to polymerize ethylene in 
CDCl.sub.3 at RT according to the general polymerization procedure using 
40 mg of catalyst. Polyethylene (25 mg) was isolated as a white powder. 
According to the .sup.1 H NMR spectrum of the reaction mixture, butenes 
were formed along with higher olefins; the major product is consistent 
with branched polyethylene 1.25 (CH.sub.2), 0.85 (CH.sub.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 
C.sub.6 D.sub.6 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 was used to polymerize ethylene in 
C.sub.6 D.sub.6 at 80.degree. C. according to the general polymerization 
procedure using 61 mg of catalyst. Polyethylene (1.39 g) was isolated. 
According to the .sup.1 H NMR spectrum of the reaction mixture, 
significant amounts of butenes and higher olefins were produced. A 
significant polyethylene --CH.sub.2 -- peak appears at 1.25 ppm. 
EXAMPLE 151 
##STR114## 
The general synthesis of nickel allyl initiators was followed using 255 mg 
of ligand, 105 mg of (C.sub.3 H.sub.5)Ni(.mu.-Cl)!.sub.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 in 
CDCl.sub.3 at RT according to the general polymerization procedure using 
45 mg of catalyst. Polyethylene (1.61 g) was isolated as a white powder. 
EXAMPLE 153 
The allyl initiator of Example 151 was used to polymerize ethylene in 
C.sub.6 D.sub.6 at RT according to the general polymerization procedure 
using 62 mg of catalyst. Polyethylene (93 mg) was isolated as a white 
powder. The .sup.1 H NMR spectrum shows the production of butenes and 
higher olefins. Polyethylene --CH.sub.2 -- resonance is identifiable at 
1.25 ppm. 
EXAMPLE 154 
The allyl initiator of Example 151 was used to polymerize ethylene in 
C.sub.6 D.sub.6 at 80.degree. C. according to the general polymerization 
procedure using 67 mg of catalyst. Polyethylene (169 mg) was isolated. 
According to the .sup.1 H NMR spectrum of the reaction mixture, the 
reaction was productive in the formation of butenes and higher olefins. 
Polyethylene --CH.sub.2 -- resonance is identifiable at 1.25 ppm. 
EXAMPLE 155 
##STR115## 
The general synthesis of nickel allyl initiators was followed using 213 mg 
of ligand, 295 mg of (H.sub.2 CC(CO.sub.2 Me)CH.sub.2)Ni(.mu.-Br)!.sub.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 in 
C.sub.6 D.sub.6 at RT according to the general polymerization procedure 
using 61 mg of catalyst. Polyethylene (1.97 g) was isolated as a white 
powder. 
EXAMPLE 157 
##STR116## 
The general synthesis of nickel allyl initiators was followed using 657 mg 
of ligand, 238 mg of (H.sub.2 CCHCMe.sub.2)Ni(.mu.-Br)!.sub.2, and 1.56 
of NaBAF. A red powder (1.88 g) was isolated. Although the free ligand 
exists as the amine, the .sup.1 H and .sup.13 C NMR spectra are consistent 
with the ligand binding to the molecule as the imine: .sup.1 H NMR 
(CD.sub.2 Cl.sub.2, 300 MHz, rt) d 8.41 (d, 1, J=5.4, N=CH), 7.8-6.8 (m, 
17, H.sub.aryl), 5.42 (d, 1, J=5.4, CEPh.sub.2), 4.80 (dd, 1, J=12.8, 6.9, 
H.sub.2 CCHCMe.sub.2), 2.95 (d, 1, J=6.7, HH'CCHCMe.sub.2), 2.03 (d, 1, 
J=13.5, HH'CCHCMe.sub.2), 0.77 (s, 6, H.sub.2 CCHCMeMe'); .sup.13 C NMR 
(CD.sub.2 Cl.sub.2, 75 MHz, rt, non-aromatic carbons only, assignments 
aided by APT spectrum) d 202.4 (C=O), 182.6 (N=CH), 109.1 (H.sub.2 
CCHCMe.sub.2), 59.7 (CHPh.sub.2), 53.2 (H.sub.2 CCHCMe.sub.2), 43.1 
(H.sub.2 CCHCMe.sub.2), 26.0 and 20.8 (H.sub.2 CCHCMeMe'). 
EXAMPLE 158 
The allyl initiator of Example 157 was used to polymerize ethylene in 
C.sub.6 D.sub.6 at RT according to the general polymerization procedure 
using 61 mg of catalyst. According to the .sup.1 H NMR spectrum, 
significant amounts of butenes and higher olefins were produced. 
EXAMPLE 159 
The allyl initiator of Example 157 was used to polymerize ethylene in 
C.sub.6 D.sub.6 at 80.degree. C. according to the general polymerization 
procedure using 63 mg of catalyst. According to the .sup.1 H NMR spectrum 
of the reaction mixture, significant amounts of butenes and higher olefins 
were produced 
For Examples 160-177 where the ligands are thiophene and furan derivatives, 
the .sup.1 H NMR spectra of the products are, in general, complex and 
include more than one species. The structural assignments of these 
complexes are therefore tentative. 
EXAMPLE 160 
##STR117## 
The general synthesis of nickel allyl initiators was followed using 115 mg 
of ligand, 50 mg of (C.sub.3 H.sub.5)Ni(.mu.-Cl)!.sub.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 in 
CDCl.sub.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 was not isolated. According to the .sup.1 H NMR spectrum of 
the reaction mixture, significant amounts of butenes and higher olefins 
were produced. 
EXAMPLE 162 
##STR118## 
The general synthesis of nickel allyl initiators was followed using 173 mg 
of ligand, 87 mg of (C.sub.3 H.sub.5)Ni(.mu.-Cl)!.sub.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 
CDCl.sub.3 at RT according to the general polymerization procedure using 
64 mg of catalyst. Polyethylene (72 mg) was isolated. The .sup.1 H NMR 
spectrum of the reaction mixture indicates that significant amounts of 
butenes and higher olefins were produced. 
EXAMPLE 164 
The allyl initiator of Example 162 was used to polymerize ethylene in 
C.sub.6 D.sub.6 at 80.degree. C. according to the general polymerization 
procedure using 68 mg of catalyst. Polyethylene (77 mg) was isolated. The 
.sup.1 H NMR spectrum of the reaction mixture indicates that significant 
amounts of butenes and higher olefins were produced. 
EXAMPLE 165 
##STR119## 
The general synthesis of nickel allyl initiators was followed using 65 mg 
of ligand, 50 mg of (H.sub.2 CCHCMe.sub.2)Ni(.mu.-Br)!.sub.2, and 213 mg 
of NaBAF. An orange powder (163 mg) was isolated. 
EXAMPLE 166 
The allyl initiator of Example 165 was used to polymerize ethylene in 
CDCl.sub.3 at RT according to the general polymerization procedure using 
40 mg of catalyst. Polyethylene (823 mg) was isolated as a white powder. 
EXAMPLE 167 
The allyl initiator of Example 165 was used to polymerize ethylene in 
C.sub.6 D.sub.6 at 80.degree. C. according to the general polymerization 
procedure using 63 mg of catalyst. Polyethylene was not isolated, however, 
the .sup.1 H NMR spectrum of the reaction mixture indicates that 
significant amounts of butenes and higher olefins were formed. 
EXAMPLE 168 
##STR120## 
The general synthesis of nickel allyl initiators was followed using 311 mg 
of ligand, 274 mg of (H.sub.2 CC(CO.sub.2 Me)CH.sub.2)Ni(.mu.-Br)!.sub.2, 
and 1.02 g of NaBAF. An orange powder (1.30 g) was isolated. 
EXAMPLE 169 
The allyl initiator of Example 168 was used to polymerize ethylene in 
CDCl.sub.3 at 80.degree. C. according to the general polymerization 
procedure using 77 mg of catalyst and 1 eqiv (31 mg) of B(C.sub.6 
F.sub.5).sub.3 cocatalyst. Polyethylene (188 mg) was isolated as a waxy 
solid. The .sup.1 H NMR spectrum of the reaction mixture indicates that 
significant amours of butenes and higher olefins were produced; the 
polyethylene --CH.sub.2 -- resonance is identifiable at 1.25 ppm. 
EXAMPLE 170 
##STR121## 
The general synthesis of nickel allyl initiators was followed using 323 mg 
of ligand, 153 mg of (C.sub.3 H.sub.5)Ni(.mu.-Cl)!.sub.2, and 1.00 g of 
NaBAF. An orange powder (1.22 g) was isolated. 
EXAMPLE 171 
##STR122## 
The general synthesis of nickel allyl initiators was followed using 329 mg 
of ligand, 239 mg of (H.sub.2 CCHCMe.sub.2)Ni(.mu.-Br)!.sub.2, and 1.02 
mg of NaBAF. A sticky red solid (742 mg) was isolated. 
EXAMPLE 172 
The allyl initiator of Example 171 was used to polymerize ethylene in 
C.sub.6 D.sub.6 at RT according to the general polymerization procedure 
using 77 mg of catalyst. Polyethylene (100 mg) was isolated. The .sup.1 H 
NMR spectrum of the reaction mixture indicates that significant amounts of 
butenes and higher olefins were produced. 
EXAMPLE 173 
##STR123## 
The general synthesis of nickel allyl initiators was followed using 327 mg 
of ligand, 272 mg of (C.sub.3 H.sub.5)Ni(.mu.-Cl)!.sub.2, and 1.01 g of 
NaBAF. An orange powder (1.42 g) was isolated. 
EXAMPLE 174 
The allyl initiator of Example 173 was used to polymerize ethylene in 
C.sub.6 D.sub.6 at RT according to the general polymerization procedure 
using 78 mg of catalyst and 2 equiv (29 mg) of BPh.sub.3 cocatalyst. 
Polyethylene was not isolated. The .sup.1 H NMR spectrum of the reaction 
mixture indicates that significant amounts of butenes and higher olefins 
were produced. 
EXAMPLE 175 
The alkyl initiator of Example 173 was used to polymerize ethylene in 
CDCl.sub.3 at 80.degree. C. according to the general polymerization 
procedure using 78 mg of catalyst and 1 equiv (31 mg) of B(C.sub.6 
F.sub.5).sub.3 cocatalyst. Polyethylene (2.39 g) was isolated. 
EXAMPLE 176 
##STR124## 
The above general procedure for nickel allyl initiators was followed using 
62 mg of ligand, 50 mg of (H.sub.2 CCHCMe.sub.2)Ni(.mu.-Br)!.sub.2, and 
213 mg of NaBAF. An orange powder (188 mg) was isolated. 
EXAMPLE 177 
The allyl initiator of Example 176 was used to polymerize ethylene in 
CDCl.sub.3 at RT according to the general polymerization procedure using 
40 mg of catalyst. No polyethylene was isolated. 
EXAMPLE 178 
##STR125## 
The general synthesis of nickel allyl initiators was followed using 462 mg 
of ligand, 153 mg of (C.sub.3 H.sub.5)Ni(.mu.-Cl)!.sub.2, and 1.00 g of 
NaBAF. A beige powder (1.68 g) was isolated. The stability of the complex 
is poor in CD.sub.2 Cl.sub.2 and THF-d.sub.8 at RT. Only broad NMR spectra 
were obtained. The above structure is therefore tentatively assigned. 
EXAMPLE 179 
The allyl initiator of Example 178 was used to polymerize ethylene in 
C.sub.6 D.sub.6 at RT according to the general polymerization procedure 
using 82 mg of catalyst. Polyethylene was not isolated. 
EXAMPLE 180 
The allyl initiator of Example 178 was used to polymerize ethylene in 
CDCl.sub.3 at 80.degree. C. according to the general polymerisation 
procedure using 82 mg of catalyst. Polyethylene (2.02 g) was isolated. 
EXAMPLE 181 
##STR126## 
The general synthesis of nickel allyl initiators was followed using 462 mg 
of ligand, 211 mg of (C.sub.3 H.sub.5)Ni(.mu.-Cl)!.sub.2, and 1.36 mg of 
NaBAF. A pale orange powder (2.16 g) was isolated. The stability of the 
complex is poor in CD.sub.2 Cl.sub.2 and THF-d.sub.8 at RT. Only broad NMR 
spectra were obtained. The above structure is therefore tentatively 
assigned. 
EXAMPLE 182 
The allyl initiator of Example 181 was used to polymerize ethylene in 
C.sub.6 D.sub.6 at RT according to the general polymerization procedure 
using 76 mg of catalyst. Polyethylene (147 mg) was isolated. 
EXAMPLE 183 
The allyl initiator of Example 181 was used to polymerize ethylene in 
CDCl.sub.3 at 80.degree. 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 
______________________________________ 
Ex. No. Ligand Ligand/Ni g. PE 
Tm, .degree.C. 
______________________________________ 
184 115 1 9.0 125 
185 116 1 2.4 -- 
186 117 2 2.7 -- 
187 118 1 5.0 -- 
______________________________________ 
##STR127## 
##STR128## 
##STR129## 
##STR130## 
EXAMPLE 188 
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 was added dropwise 2.77 g 
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 washing with 
methanol and THF to remove excess 2-anthranilamide. TLC (5:1 hexane:ethyl 
acetate) showed a single new band. The dried product weighed 3.5 g. .sup.1 
H NMR (DMSO, .delta. in ppm):9.82(s, 1H) ;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-Diphenylacetaldehyde (0.4906 g) was dissolved in 30 ml methanol. To 
this hot solution was added 0.4881 g 1-amino-9-fluorenone (in 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 0.4 g. The 
.sup.1 H, .sup.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. .sup.1 H NMR (CD.sub.2 
Cl.sub.2, 300 MHz, rt) d 9.25 (d, 1, J=12.1, NH), 7.6-6.85 (m, 18, 
H.sub.aryl and CH=CPh.sub.2); .sup.13 C NMR (CD.sub.2 Cl.sub.2, 75 MHz, 
rt, assignments were aided by an APT spectrum) d 194.0 (C=O), 144.6, 
143.1, 142.7, 141.2, 137.7, 134.7 121.3 and 115.15 (C.sub.aryl not 
attached to hydrogen and =CPh.sub.2), 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 
(C.sub.aryl attached to hydrogen and =CHNHAr). 
EXAMPLE 190 
Synthesis of 63 
1-Aminoanthraquinone (2.2323 g) was dissolved in a 1:1 mixture of methanol 
and THF. To the hot solution was added 1.9625 g 1,1-diphenylacetaldehyde. 
Then 8 drops of formic acid was added as catalyst. After refluxing 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 was 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 was also obtained by 
silica gel chromatography to give a purple solid. Yield 1.2 g. .sup.1 H 
NMR (CD.sub.2 Cl.sub.2, .delta. in ppm):11.75(d, 1H);8.20(m, 
2H);7.25-7.85(m, 16H). 
EXAMPLE 191 
Synthesis of 54 
1,1-Diphenylacetaldehyde (3.9250 g) was dissolved in 30 ml anhydrous 
methanol. To this refluxing solution was added 2.7230 g 2-anthranilamide 
(in methanol). Soon a yellow precipitate formed. After all the 
2-anthranilamide was added, heating and stirring were continued for 
another hour. When cooled, the solid was isolated by filtering. The solid 
was then resuspended in methanol, stirred and then filtered. Yield 5.1 g. 
The .sup.1 H, .sup.13 C, and APT spectra are consistent with the existence 
of the product as the enamine structure shown above: .sup.1 H NMR 
(THF-d.sub.8, 300 MHz, rt, assignments were aided by an APT spectrum) 
.delta. 10.86 (br d, 1, J =12.10, NH-CH=CPh.sub.2), 7.60-6.85 (m, 16, 
H.sub.aryl, CH=CPh.sub.2, C(O)NHH'), 6.60 (br s, 1, C(O)NHH'); .sup.13 C 
NMR (THF-d.sub.8, 75 MHz, rt, assignments were aided by an APT spectrum) 
.delta. 171.9 (C=O), 145.9, 143.4, 139.7, 120.0 and 116.6 (C.sub.aryl not 
attached to hydrogen and =CPh.sub.2), 113.4, 131.1, 129.4, 128.8, 127.4, 
125.9, 124.9, 117.8 and 113.4 (C.sub.aryl attached to hydrogen and 
=CHNAr). 
EXAMPLE 192 
Synthesis of 56 
1,1-Diphenylacetaldehyde (4.0138 g) was dissolved in 20 ml anhydrous 
methanol. To this hot solution was added 3.0918 g methyl anthranilate (in 
methanol). The color of the solution changed from colorless to yellow as 
soon as two components were mixed. After adding all the methyl 
anthranilate, the heat was turned off. During cooling, a yellow 
precipitate began to form. The precipitate was collected by filtering 
followed by washing with methanol. After recrystallization in methanol, 
2.6 g product was obtained. 
The .sup.1 H, .sup.13 C, and APT spectra are consistent with the existence 
of the product as the enamine structure shown above. In addition, this 
structure was confirmed by X-ray crystallography. .sup.1 H NMR (CD.sub.2 
Cl.sub.2, 300 MHz, rt) .delta. 9.94 (br d, 1, J=11.73, NH), 8.05-6.75 (m, 
15, H.sub.aryl and =CHNHAr), 3.78 (s, 3, OMe); .sup.13 C NMR (CD.sub.2 
Cl.sub.2, 75 MHz, rt, assignments were aided by an APT spectrum) .delta. 
168.0 (C=O), 145.4, 141.9, 138.4, 120.9 and 112.1 (C.sub.aryl not attached 
to hydrogen and CH=CPh.sub.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.sub.aryl attached to hydrogen and 
CH=CPh.sub.2), 51.8 (OMe). 
EXAMPLE 193 
Synthesis of 55 
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 refluxing solution was added dropwise 1.7729 g 
2,6-diisopropylaniline. When the addition was complete, 4 drops 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 2.5 g of dried product. .sup.1 H NMR (CD.sub.2 Cl.sub.2, 
.delta. in ppm): 9.51(s, 1H);9.05(d, 2H);9.20(s, 1H);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 
##STR131## 
The general synthesis of nickel allyl initiators was followed using 136 mg 
of ligand, 53 mg of (C.sub.3 H.sub.5)Ni(.mu.-Cl)!.sub.2, and 342 mg of 
NaBAF. A yellow powder (430 mg) was isolated. 
EXAMPLE 195 
The allyl initiator of Example 194 was used to polymerize ethylene in 
C.sub.6 D.sub.6 at 80.degree. C. according to the general polymerization 
procedure using 64 mg of catalyst. Polyethylene (104 mg) was isolated. The 
.sup.1 H NMR spectrum of the reaction mixture showed that significant 
amounts of butones and higher olefins were produced. 
EXAMPLE 196 
##STR132## 
The general synthesis of nickel allyl initiators was followed using 129 mg 
of ligand, 51 mg of (C.sub.3 H.sub.5)Ni(.mu.-Cl)!.sub.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 in 
CDCl.sub.3 at 60.degree. C. according to the general polymerization 
procedure using 24 mg of catalyst. The ethylene pressure was initially 1.2 
MPa and was increased to 6.9 MPa after 1 h. A few mg's of polyethylene was 
produced. The .sup.1 H NMR spectrum of the reaction mixture showed that 
significant amounts of butenes and higher olefins were produced. 
EXAMPLE 198 
##STR133## 
The general synthesis of nickel allyl initiators was followed using 136 mg 
of ligand, 49 mg of (C.sub.3 H.sub.5)Ni(.mu.-Cl)!.sub.2, and 309 mg of 
NaBAF. An orange powder (380 mg) was isolated. 
EXAMPLE 199 
The allyl initiator of Example 198 was used to polymerize ethylene in 
C.sub.6 D.sub.6 at RT at 5.2 MPa according to the general polymerization 
procedure using 63 mg of catalyst. Polyethylene (29 mg) was isolated. The 
.sup.1 H NMR spectrum of the reaction mixture showed that significant 
amounts of butenes and higher olefins were produced. 
EXAMPLE 200 
##STR134## 
The general synthesis of nickel allyl initiators was followed using 111 mg 
of ligand, 50 mg of (C.sub.3 H.sub.5)Ni(.mu.-Cl)!.sub.2, and 328 mg of 
NaBAF. An orange powder (347 mg) was isolated. 
EXAMPLE 202 
The allyl initiator of Example 201 was used to polymerize ethylene in 
CDCl.sub.3 at 60.degree. C. according to the general polymerization 
procedure using 23 mg of catalyst. The ethylene pressure was initially 1.4 
MPa and was increased to 6.9 MPa after 1 h. A few mg's of polyethylene was 
produced. The .sup.1 H NMR spectrum of the reaction mixture showed that 
significant amounts of butenes and higher olefins were produced. 
EXAMPLE 203 
##STR135## 
Using 5.47 g of 1,1-diphenylacetaldehyde and 3.60 g of 2,6-dimethylaniline, 
5.79 g of an orange powder was obtained following a synthesis analogous to 
that of the 2,6-diisopropylaniline derivative given above. The .sup.1 H, 
.sup.13 C, and APT spectra are consistent with the existence of the 
product as the enamine structure shown above: .sup.1 H NMR (CDCl.sub.3, 
300 MHz, rt) .delta. 7.6-7.0 (m, 13, H.sub.aryl), 6.88 (d, 1, J=12.1, 
ArNHCH=CPh.sub.2), 5.47 (d, 1, J =12.1, ArNHCH=CPh.sub.2), 2.37 (s, 6, 
C.sub.6 H.sub.3 -Me.sub.2); .sup.13 C NMR (CDCl.sub.3, 75 MHz, rt, 
assignments aided by an APT spectrum) .delta. 142.0, 140.7, 138.9 and 
131.1 (Ph: C.sub.ipso ; Ph': C.sub.ipso ; Ar: C.sub.ipso and C.sub.o), 
131.6, 130.6, 129.3, 128.9, 128.3, 126.9, 125.4, 124.8 and 123.8 (Ph: 
C.sub.o, C.sub.m, C.sub.p ; Ph': C.sub.o, C.sub.m, C.sub.p ; Ar: C.sub.m, 
C.sub.p ; CH=CPh.sub.2), 114.0 (CH=CPh.sub.2), 13.8 (C.sub.6 H.sub.3 
-Me.sub.2). 
EXAMPLE 204 
##STR136## 
Using 5.43 g of 1,1-diphenylacetaldehyde and 2.71 g of aniline, 5.68 g of 
yellow powder was obtained following a synthesis analogous to that of the 
2,6-diisopropylaniline derivative given above. The .sup.1 H, .sup.13 C, 
and APT spectra are consistent with the existence of the product as the 
enamine structure shown above: .sup.1 H NMR (CDCl.sub.3, 300 MHz, rt) 
.delta. 7.6-6.8 (m, 15, H.sub.aryl), 7.18 (d, 1, J=12.1, 
PhNHCH=CPh.sub.2), 6.12 (d, 1, J =11.8, PhNHCH=CPh.sub.2); .sup.13 C NMR 
(CDCl.sub.3, 75 MHz, rt, assignments were aided by an APT spectrum) 
.delta. 142.7, 141.8 and 138.5 (Ph: C.sub.ipso ; Ph': C.sub.ipso ; Ph": 
C.sub.ipso), 130.5, 129.6, 129.3, 128.4, 127.2, 126.2, 125.5, 124.8, 120.0 
and 113.9 (Ph: C.sub.o, C.sub.m, C.sub.p ; Ph': C.sub.o, C.sub.m, C.sub.p 
; Ph": C.sub.o, C.sub.m, C.sub.p ; CH=CPh.sub.2), 117.7 (CH=CPh.sub.2). 
EXAMPLE 205 
##STR137## 
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 .about.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 
was then dissolved in Et.sub.2 O and stirred overnight over Na.sub.2 
SO.sub.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 .sup.1 H and .sup.13 C are consistent with the product existing as the 
cyclized diamine rather than as the diamine. Note: Literature precedent 
for this cyclization reaction exists, 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.!: .sup.1 H NMR (CDCl.sub.3, 300 MHz, rt) .delta. 6.9-6.5 (m, 6, 
H.sub.aryl), 4.58 (s, 2, NH), 2.20 and 1.62 (s, 6 each, Me, Me'); .sup.13 
C NMR (CDCl.sub.3, 75 MHz, rt) .delta. 141.7, 127.1 and 122.3 (Ar: 
C.sub.ipso, C.sub.o, C.sub.o '), 122.6, 119.8, 114.9 (Ar: C.sub.m, C.sub.m 
', C.sub.p), 82.0 (--OC(Me)NH--), 22.1 and 16.7 (Me, Me'). 
EXAMPLE 206 
##STR138## 
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 Et.sub.2 
O. 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 was then stirred overnight. Some 
of the product precipitate out of the Et.sub.2 O solution along with the 
LiCl. Some of the Et.sub.2 O was removed in vacuo and enough THF was added 
to dissolve the product. The solution was filtered through a frit with 
Celite, the Celite was washed with THF, and the solvent was removed in 
vacuo. The product was washed with pentate and pumped dry to give 20.72 g 
of an off-white powder: .sup.1 H NMR (CDCl.sub.3, 300 MHz, rt) .delta. 
9.26 (br s, 2, NH), 7.23-7.04 (m, 6, H.sub.aryl), 2.94 (septet, 4, 
CHMe.sub.2), 1.09 (d, 24, CEMe.sub.2). 
EXAMPLE 207 
##STR139## 
Following the synthetic procedure of the above example, 7.49 g of oxalyl 
chloride and 15.00 g of lithium 2,6-dimethylanilide was used to synthesize 
23.98 g of product, which was isolated as an off-white powder: .sup.1 H 
NMR (CDCl.sub.3, 300 MHz, rt) .delta. 9.53 (br 2, 2, NH), 7.00-6.86 (m, 6, 
H.sub.aryl), 2.10 (s, 12, Me). 
EXAMPLE 208 
##STR140## 
Formic acid catalyst (.about.1 mL) was added to a methanol solution of 
diphenylacetaldehyde (4.44 mL) and 2,6-diisopropylaniiine (3.18 mL). After 
.about.15 minutes of stirring, a white precipitate formed. The reaction 
mixture was stirred for several days before the precipitate was collected 
on a frit and washed with methanol. The product was then dissolved in 
Et.sub.2 O and stirred over Na.sub.2 SO.sub.4 overnight. The solution was 
filtered through a frit with Celite and the solvent was removed in vacuo 
to yield the product. The .sup.1 H, .sup.13 C, and APT spectra are 
consistent with the existence of the product as the enamine structure 
shown above: .sup.1 H NMR (CD.sub.2 Cl.sub.2, 300 MHz, rt) 8 7.6-7.0 (m, 
13, H.sub.aryl), 6.71 (d, 1, J=12.1, =CHNHAr), 5.37 (d, 1, J=12.5, NHAr), 
3.34 (septet, 2, J=6.9, CHMe.sub.2), 1.25 (d, 12, J=7.0, CHMe.sub.2); 
.sup.13 C NMR (CD.sub.2 Cl.sub.2, 300 MHz, rt, assignments were aided by 
an APT spectrum) .delta. 144.9 (Ar: C.sub.o), 142.5, 139.3 and 138.5 (Ar: 
C.sub.ipso, Ph: C.sub.ipso, Ph': C.sub.ipso), 133.9, 130.9, 129.7, 128.6, 
127.2, 126.2, 125.4, 124.7 and 124.0 (Ph: C.sub.o, C.sub.m, C.sub.p ; Ph': 
C.sub.o, C.sub.m, C.sub.p ; Ar: C.sub.m, C.sub.p, Ph.sub.2 C=CH), 113.4 
(Ph.sub.2 C=CH), 28.6 (CHMe.sub.2), 23.9 (CHMe.sub.2). 
EXAMPLES 209-217 
The imines in the following table were synthesized using Procedures A and B 
below. Details are shown in the Table. 
A. Formic acid catalyst was added to a methanol solution of the aldehyde 
and the aniline. The reaction mixture was stirred and the resulting 
precipitate was collected on a frit and washed with methanol. The product 
was then dissolved in Et.sub.2 O or CH.sub.2 Cl.sub.2 and stirred over 
Na.sub.2 SO.sub.4 overnight. The solution was filtered through a frit with 
Celite and the solvent was removed in vacuo to yield the product. 
B. A CH.sub.2 Cl.sub.2 solution of the aldehyde and the aniline was stirred 
over sodium sulfate. The solution was filtered through a frit with Celite 
and the solvent was removed in vacuo. 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 
##STR141## Procedure A. .sup.1 H NMR (CDCl.sub.3, 300 MHz, rt) 
.delta. 8.97 (s, 1, CHN), 8.43 (dd, 1, J=7.8, 1.6, 
H.sub.aryl), 7.64 (dd, 1, J=7.6, 1.3, H.sub.aryl), 
7.55 (t, 1, J=7.2, H.sub.aryl), 7.46 (td, 1, J=7.4, 
1.7, H.sub.aryl), 7.37 (s, 2, H.sub.aryl), 1.37 (s, 
9, CMe.sub.3), 1.28 (s, 18, CMe.sub.3), 1.21 (s, 9, 
CMe.sub.3). 
210 
##STR142## Procedure A. .sup.1 H NMR (CDCl.sub.3, 300 MHz, rt) 
.delta. 15.30 (s, 1, OH), 9.09 (s, 1, NCH), 8.1-7.2 
(m, 9, H.sub.aryl), 3.12 (septet, 2, CHMe.sub.2), 
1.25 (d, 12, CHMe.sub.2); .sup.13 C 
NMR (CDCl.sub.3, 75 MHz, rt) .delta. 161.7 (CN). 
211 
##STR143## Procedure A. .sup.1 H NMR (CDCl.sub.3, 300 MHz, rt) 
.delta. 15.3 (s, 1, OH), 9.23 (s, 1, NCH), 8.4-7.1 
(m, 9, H.sub.aryl), 2.41 (s, 6, Me). 
212 
##STR144## Procedure A. .sup.1 H NMR (CDCl.sub.3, 300 MHz, rt) 
.delta. 14.15 (s, 1, OH), 8.43 (s, 1, NCH), 7.7-7.1 
(m, 5, H.sub.aryl), 2.35 (s, 6, Me). 
213 
##STR145## Procedure A. .sup.1 H NMR (CDCl.sub.3, 300 MHz, rt) 
.delta. 12.27 (s, 1, OH), 8.85 (NCH), 7.6-6.9 (m, 
4, H.sub.aryl); .sup.13 C NMR (CDCl.sub.3, 75 MHz, 
rt) .delta. 170.6, 161.5, 134.9, 133.3, 119.5, 
118.7 and 117.8 (NCH, C.sub.aryl excluding C.sub.6 
F.sub.5 resonances). 
214 
##STR146## Procedure A. .sup.1 H NMR (CDCl.sub.3, 300 MHz, rt) 
.delta. 8.20 (s, 1, NCH), 8.0- 7.0 (m, 8, 
H.sub.aryl), 3.00 (septet, 2, CHMe.sub.2), 1.21 (d, 
12, CHMe.sub.2); .sup.13 C NMR (CDCl.sub.3, 75 MHz, 
rt) .delta. 161.9 (NCH), 149.3, 137.6, 136.1, 
131.3, 128.8, 128.5, 124.1 and 123.0 (C.sub.aryl), 
28.0 (CHMe.sub.2), 23.5 (CHMe.sub.2). 
215 
##STR147## Procedure A. .sup.1 H NMR (CDCl.sub.3, 300 MHz, rt) 
.delta. 8.48 (s, 1, NCH), 7.35- 6.95 (m, 3, 
H.sub.aryl), 2.22 (s, 3, Me); .sup.13 C NMR 
(CDCl.sub.3, 300 MHz, rt) .delta. 153.9 (NCH), 
148.2, 130.4, 128.8, 127.6, 125.5 and 122.6 
(C.sub.aryl excluding C.sub.6 F.sub.5 resonances), 
18.4 (Me). 
216 
##STR148## Procedure B. .sup.1 H NMR (CDCl.sub.3, 300 MHz, rt) 
.delta. 7.99 (s, 1, CHN), 7.7- 6.5 (m, 6, 
H.sub.aryl), 3.00 (septet, 2, CHMe.sub.2), 1.19 (d, 
12, CHMe.sub.2); .sup.13 C NMR (CDCl.sub.3, 75 MHz, 
rt) .delta. 152, 150.4, 149, 145.5, 137.8, 124.3, 
123.0, 115.0 and 112.0 (NCH and C.sub.aryl), 27.9 
(CHMe.sub.2), 23.6 (CHMe.sub.2). 
217 
##STR149## Procedure B. .sup.1 H NMR (CDCl.sub.3, 300 MHz, rt) 
.delta. 8.35 (s, 1, CHN), 7.6- 7.1 (m, 6, 
H.sub.aryl), 3.08 (septet, 2, CHMe.sub.2), 1.25 (d, 
12, CHMe.sub.2); .sup.13 C NMR (CDCl.sub.3, 75 MHz, 
rt) .delta. 154.9, 148.5, 142.5, 137.8, 131.6, 
130.1, 127.6, 124.2 and 122.9 (NCH and C.sub.aryl), 
27.9 (CHMe.sub.2), 23.4 (CHMe.sub.2). 
__________________________________________________________________________ 
EXAMPLE 218 
In a dry and oxygen free atmosphere, the allyl initiator of Example 168 (16 
mg) was dissolved in dry CH.sub.2 Cl.sub.2 (2 ml). 
5-Ethylidene-2-norbornene (1.8 g) was added. The orange solution warmed 
and darkened. After stirring for 17 hours the reaction was quenched by 
addition of methanol and the solid polymer filtered, washed well with 
methanol and dried. Yield=1.6 g (89%). .sup.1 H-NMR data confirmed that 
this was an addition polymer. 
EXAMPLE 219 
Synthesis of 107 
2,6-Dimethylthiophenol (3.0 g) was mixed with 30 ml THF. Then 0.87 g NaOH 
was added. The mixture was stirred until all the NaOH has dissolved. THF 
was removed under vacuum. To the solid was added 40 ml DMF and 4.02 g of 
the bis toluenesulfonate ester of ethylene glycol. The mixture was 
refluxed for 5-6 h. DMF was removed by rotary evaporator to give a white 
residue. Water was added to the residue and the mixture extracted with 
CH.sub.2 Cl.sub.2. After removing CH.sub.2 Cl.sub.2, a white solid 
remained. TLC (hexane) showed two bands. The second band from a silica-gel 
column was the desired product. 
.sup.1 H NMR (CDCl.sub.3, .delta. in ppm): 2.43 (s, 12H); 2.72(s, 4H); 
7.10(m, 6H). 
EXAMPLE 220 
Synthesis of 116 
9-Anthraldehyde (2.06 g) was dissolved in a minimum amount of THF, then 
1.37 g anthranilic acid was added. Four drops of formic acid were added as 
catalyst. The mixture was refluxed for 7h. TLC (5:1 hexane:ethyl acetate) 
gave 3 bands. The second band is the desired product as determined by 
.sup.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.sub.3 /50 ml toluene. To this boiling solution was added 
dropwise 3.5 g 2,6-diisopropylaniline 3-4 drops of formic acid as a 
catalyst. The solution was refluxed for 13h. After removing all the 
solvent, a dark brown thick oil was left. On standing, the oil 
crystallized. The crystals were washed with methanol. 
.sup.1 H NMR (CDCl.sub.3, .delta. in ppm): 1.40 (d, 12H); 3.35(p, 2H); 
7.40(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 was (2.41 g) was dissolved in 50 ml toluene, and 
to the hot solution was added 2.0 g of methyl anthranilate (in THF) 
dropwise. After refluxing for 6h, a yellow solid precipitated. The solid 
was isolated by filtration, followed by washing with methanol. The solid 
was dissolved in 2-3 ml CDCl.sub.3 and after column separation, 9olden 
yellow crystals were obtained. .sup.1 H NMR showed it is a pure product. 
.sup.1 H NMR (DMF-d7, .delta. in ppm): 4.20(s, 3H); 6.50(d, 1H); 6.S2(t, 
1H); 7.20(t, 1H); 7.63(t, 2H); 7.80(t, 2H); 8.10(s, 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 (16 
mg) was dissolved in dry CH.sub.2 Cl.sub.2 (2 ml). Dicyclopentadiene (2 
ml) was added. The orange solution darkened. After stirring for 72 h the 
volatiles were removed from the reaction under vacuum. After addition of 
methanol the solid polymer precipitated and was filtered, washed well with 
methanol and dried. Yield=0.29 g (15%). The product was insoluble at room 
temperature in common organic solvents.