FIELD OF THE INVENTION The invention concerns novel ho o- and copolymers of ethylene and/or one or more acyclic olefins, and/or selected cyclic. olefins, and optionally selected ester, carboxylic acid, or other functional group containing olefins as comonomers; selected transition metal containing polymerization catalysts; and processes for making such polymers, intermediates for such catalysts, and new processes for making such catalysts. Also disclosed herein is a process for the production of linear alpha-olefins by contacting ethylene with a nickel compound of the formula [DAB]NiX ₂ wherein DAB is a selected α-diimine and X is chlorine, bromine, iodine or alkyl, and a selected Lewis or Bronsted acid, or by contacting ethylene with other selected α-diimine nickel complexes BACKGROUND OF THE INVENTION

Homo- and copolymers of ethylene (E) and/or one or more acyclic olefins, and/or cyclic olefins, and/or substituted olefins, and optionally selected olefinic esters cr carboxylic acids; and other types of monomers, are useful materials, being used as plastics for packaging materials, molded items, films, etc., and as elastomers for molded goods, belts of various types, in tires, adhesives, and for other uses. It is well

known in the art that the structure of these various polymers, and hence their properties and uses, are highly dependent on the catalyst and specific conditions used during their synthesis. In addition to these factors, processes in which these types of polymers can be made at reduced cost are also important. Therefore, improved processes for making such (new) polymers are of interest. Also disclosed herein are uses for the novel polymers. α-Olefins are commercial materials being particularly useful as monomers and as chemical intermediates. For a review of α-olefins, including their uses and preparation, see B. Elvers, et al . , Ed., Ulimann's Encyclopedia of Industrial Chemistry, 5th Ξd. , Vol. A13, VCH Verlagsgesellschaft mbH, Weinheim, 1989, p. 238-251. They are useful as chemical intermediates and they are often made by the oligomerization of ethylene using various types of catalysts. Therefore catalysts which are capable or forming α-olefins from ethylene are constantly sought.

SUMMARY OF THE INVENTION This invention concerns a polyolefin, which contains about 80 to about 150 branches per 1000 methylene groups, and which contains for every 100 branches that are methyl, about 30 to about 90 ethyl branches, about 4 to about 20 propyl branches, about 15 to about 50 butyl branches, about 3 to about 15 amyl branches, and about 30 to about 140 hexyl or longer branches . This invention also concerns a polyolefin which contains about 20 to about 150 branches per 1000 methylene groups, and which contains for every 100 branches that are methyl, about 4 to about 20 ethyl branches, about 1 to about 12 propyl branches, about 1 to about 12 butyl branches, about 1 to about 10 amyl branches, and 0 to about 20 hexyl or longer branches.

Disclosed herein is a polymer, consisting essentially of repeat units derived from the monomers,

ethylene and a compound of the formula

CH ₂ =CH(CH ₂ ) _m C0 ₂ R ¹ , wherein R ¹ is hydrogen, hydrocarbyl or substituted hydrocarbyl, and m is 0 or an integer from 1 to 16, and which contains about 0.01 to about 40 mole percent of repeat units derived from said compound, and provided that said repeat units derived from said compound are in branches of the formula -CH (CH ₂ ) _n C0 ₂ R ¹ , in about 30 to about 70 mole percent of said branches n is 5 or more, in about 0 to about 20 mole percent n is 4, in about 3 to 60 mole percent n is 1, 2 and 3, and in about 1 to about 60 mole percent n is 0.

This invention concerns a polymer of one or more alpha-olefins of the formula CH ₂ =CH (CH ) _a H wherein a is an integer of 2 or more, which contains the structure (XXV)

p35 R^6

I I —CH-CH ₂ -CH— (XXV)

wherein R ³⁵ is an alkyl group and R ³⁶ is an alkyl group containing two or more carbon atoms, and provided that

R ³⁵ is methyl in about 2 mole percent or more of the total amount of (XXV) in said polymer.

This invention also includes a polymer of one or more alpha-olefins of the formula CH =CH(CH ) _a H wherein a is an integer of 2 or more, wherein said polymer contains methyl branches and said methyl branches comprise about 25 to about 75 mole percent of the total branches.

This invention also concerns a polyethylene containing the structure (XXVII) in an amount greater than can be accounted for by end groups, and preferably at least 0.5 or more of such branches per 1000 methylene groups than can be accounted for by end groups.

CH ₃

I — CH ₂ -CH-CH ₂ CH ₃ (XXVII)

This invention also concerns a polypropylene containing one or both of the structures (XXVIII) and (XXIX) and in the case of (XXIX) in amounts greater than can be accounted for by end groups. Preferably at least 0.5 more of (XXIX) branches per 1000 methylene ^■ groups than can be accounted for by end groups, and/or at least 0.5 more of (XXVIII) per 1000 methylene groups are present in the polypropylene.

CH, I _/ CH CH ₂ "CH ₃

__ _C I _H _ (XXVIII) CH ₃

I

—CH ₂ CH ₂ -CH-CH ₃ (XXIX)

Also described herein is an ethylene homopolymer with a density of 0.86 g/ml or less.

Described herein is a process for the polymerization of olefins, comprising, contacting a transition metal complex of a bidentate ligand selected from the group consisting of

(VIII)

(XXX)

(XXIII)

(XXXII) with an oiefin wherein: said oiefin is selected from the group consisting of ethylene, an oiefin of the formula R ¹⁷ CH=CH _: or R ^* CH=CHR ¹⁷ , cyclobutene, cyclopentene, norbornene, or substituted norbornene; said transition metal is selected from the group consisting of Ti, Zr, Sc , V, Cr, a rare earth metal, Fe, Co, Ni or Pd;

R' and R ⁵ are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;

R ^~ and R ⁴ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R ³ and R ⁴

taken together are hydrocarbylene substituted hydrocarbylene to form a carbocyclic ring;

R is hydrocarbyl or substituted hydrocarbyl, and R is hydrogen, hydrocarbyl or substituted hydrocarbyl or R ⁴⁴ and R ²⁸ taken together form a ring; R is hydrocarbyl or substituted hydrocarbyl, and R ²⁹ is hydrogen, substituted hydrocarbyl or hydrocarbyl, or R ⁴⁵ and R ²⁹ taken together form a ring; each R ³⁰ is independently hydrogen, substituted hydrocarbyl or hydrocarbyl, or two of R taken together form a ring;

R ²⁰ and R ²³ are independently hydrocarbyl or substituted hydrocarbyl;

R ¹ and R" are each in independently hydrogen, hydrocarbyl or substituted hydrocarbyl; each R ¹ is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said oiefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms; n is 2 or 3 ;

R ¹ is hydrogen, hydrocarbyl or substituted hydrocarbyl,- and provided that : said transition metal also has bonded to it a ligand that may be displace by said oiefin or add to said oiefin; when M is Pd, said bidentate ligand is (VIII) , (XXXII) or (XXIII) ; when M is Pd a diene is not present; and when norbornene or substituted norbornene is used no other oiefin is present .

Described herein is a process for the copolymerization of an oiefin and a fluorinated oiefin, comprising, contacting a transition metal complex of a bidentate ligand selected from the group consisting of

(VIII )

with an oiefin, and a fluorinated oiefin wherein: said oiefin is selected from the group consisting of ethylene and an oiefin of the formula R ¹⁷ CH=CH ₂ or R ¹⁷ CH=CHR ¹⁷ ; said transition metal is selected from the group consisting of Ni and Pd; said fluorinated oiefin is of the formula

H ₂ C=CH(CH ₂ ) _a R _£ R ⁴² ; a is an integer of 2 to 20; R _f is perfluoroalkylene optionally containing one or more ether groups; R ⁴ is fluorine or a functional group;

R and R are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it; R ³ and R ⁴ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R and R ^"* taken together are hydrocarbylene substituted hydrocarbylene to form a carbocyclic ring; each R is independently saturated hydrocarbyl ,- and provided that said transition metal also has bonded to it a ligand that may be displaced by said oiefin or add to said oiefin.

This invention also concerns a copolymer of an oiefin of the formula R ¹⁷ CH=CHR ¹⁷ and a fluorinated oiefin of the formula H ₂ C=CH(CH ₂ ) _a R _f R ⁴² , wherein: each R ¹⁷ is independently hydrogen or saturated hydrocarbyl,-

a is an integer of 2 to 20; R _f is perfluoroalkylene optionally containing one or more ether groups; and

R is fluorine or a functional group; provided that when both of R ^x ' are hydrogen and R ⁴² is fluorine, R _f is -(CF ₂ ) _b - wherein b is 2 to 20 or perfluoroalkylene containing at least one ether group.

Described herein is a process for the polymerization of olefins, comprising, contacting, at a temperature of about -100°C to about +200 ^C C: a first compound , which is a neutral Lewis acid capable cf abstracting either Q ^" or S ^" to form WQ ^" or WS ^" , provided that the anion formed is a weakly coordinating anion; or a cationic Lewis cr Bronsted acid whose counterion is a weakly coordinating anion; a second compound of the formula

(χι :

and one or more monomers selected from the group consisting of ethylene, an oiefin of the formula R ¹ CH=CH ₂ or R ^* CH=CHR ¹⁷ , cyclobutene, cyclcpentene, substituted norbornene, or norbornene; wherein:

M is Ti, Zr, Sc, V, Cr, a rare earth metal, Fe, Co, Ni or Pd the oxidation state; y + z = m

R ² and R ⁵ are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;

R ³ and R ⁴ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R and R ⁴ taken together are hydrocarbylene or substituted hydrocarbylene to form a ring; each R is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said oiefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms; Q is alkyl, hydride, chloride, iodide, or bromide;

S is alkyl, hydride, chloride, iodide, or bromide,- and provided that : when norbornene or substituted norbornene is present, no other monomer is present; when M is Pd a diene is not present; and except when M is Pd, when both Q and S are each independently chloride, bromide or iodide W is capable of transferring a hydride or alkyl group to M. This invention includes a process for the production of polyolefins, comprising contacting, at a temperature of about -100°C to about +200°C, one or more monomers selected from the group consisting of ethylene, an oiefin of the formula R ^" CH=CH ₂ or

R ¹⁷ CH=CHR ^* ', cyclobutene, cyclopentene, substituted norbornene, and norbornene; with a compound of the formula

II; (III) TV)

or

(VII) wnerem: R ^* and R are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it ;

R ³ and R ⁴ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R and R ⁴ taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;

T ^~ is hydrogen, hydrocarbyl not containing clefir.ic or acetylenic bonds, R ¹⁵ C'=0)- or R ¹⁵ OC(=0)- _; n is 2 or 3;

Z is a neutral Lewis base wherein the donating atom s nitrogen, sulfur or oxygen, provided that if the donating atom is nitrogen then the pKa of the conjugate acid of that compound is less than about 6;

X is a weakly coordinating anion; R ^1S is hydrocarbyl not containing olefinic or acetylenic bonds; each R ¹ is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said oiefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms; M is Ni (II) or Pd(II) ; each R ¹⁶ is independently hydrogen or alkyl containing 1 to 10 carbon atoms; n is 1, 2, or 3; R is hydrocarbyl; and

T ² is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, hydrocarbyl substituted with keto or ester groups but not containing olefinic or acetylenic bonds, R ^1S C(=0)- or R ¹⁵ OC(=0)-,- and provided that : when M is Pd a diene is not present; and when norbornene or substituted norbornene is used no other monomer is present.

This invention includes a process for the production of polyolefins, comprising contacting, at a temperature of about -100°C to about +200°C, one or more monomers selected from the group consisting of ethylene, an oiefin of the formula R ¹ CH=CH ₂ or R ¹⁷ CH=CHR ¹⁷ , cyclobutene, cyclopentene, substituted norbornene, and norbornene; with a compound of the formula

(XVII) (XVIII) or

(XIII)

wherein:

R 44 is hydrocarbyl or substituted hydrocarbyl, and R .2"8 is hydrogen, hydrocarbyl or substituted hydrocarbyl or R and R taken together form a ring;

R 45 is hydrocarbyl or substituted hydrocarbyl, and R ^" is hydrogen, substituted hydrocarbyl or hydrocarbyl, or R and R" taken together form a ring; each R is independently hydrogen, substituted hydrocarbyl or hydrocarbyl , or two of R taken together form a ring; each R" is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said oiefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms,-

R" ^u and R ^* are independen ly hydrocarbyl or substituted hydrocarbyl;

R ^* " and R" are each in independently hydrogen, hydrocarbyl cr substituted hydrocarbyl;

T ¹ is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, R ¹⁵ C(=0)- or R ^1" CC(=0)-;

Z is a neutral Lewis base wherein the donating atom is nitrogen, sulfur or oxygen, provided that if the donating atom is nitrogen then the pKa of the conjugate acid of that compound is less than about 6; and

X is a weakly coordinating anion,- and provided tha : when M is Pd or (XVIII) is used a dier.e is not present ,- and in (XVII) M is not Pd.

This invention includes a process for the production of polyolefins, comprising contacting, at a temperature of about -100°C to about +200°C, cr.e or more monomers selected from the group consisting of ethylene, an oiefin of the formula R ¹⁷ CH=CH ₂ or R ¹⁷ CH=CHR ¹⁷ , 4-vinylcyclohexene, cyclobutene, cyclopentene, substituted norbornene, and norbornene; with a compound of the formula

(XVIII)

wherein: R ²⁰ and R ²³ are independently hydrocarbyl or substituted hydrocarbyl;

R ^:: and R ²² are each in independently hydrogen, hydrocarbyl or substituted hydrocarbyl;

T ¹ is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, R ¹⁵ C (=0)- or R ¹⁵ OC(=0)-

Z is a neutral Lewis base wherein the donating atom is nitrogen, sulfur or oxygen, provided that if the donating atom is nitrogen then the pKa of the conjugate acid of that compound is less than about 6; X is a weakly coordinating anion;

R ¹ ^ is hydrocarbyl not containing olefinic or acetylenic bonds; each R ¹⁷ is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said oiefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms; M is Ni (II) or Pd(II) ;

T ² is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, hydrocarbyl substituted with keto or ester groups but not containing olefinic or acetylenic bonds, R ¹⁵ C(=0) - or R ¹⁵ OC(=0) - _; and provided that : when M is Pd a diene is not present; and when norbornene or substituted norbornene is used no other monomer is present.

Described herein is a process for the production for polyolefins, comprising contacting, at a temperature of about -100°C to about +200°C, a first compound W, which is a neutral Lewis acid capable of abstracting either Q ^" or S ^" to form WQ ^' or WS ^" , provided that the anion formed is a weakly coordinating anion; or a cationic Lewis or Bronsted acid whose counterion is a weakly coordinating anion; a second compound of the fcrmula

(XVII)

and one or more monomers selected frotu trie group consisting of ethylene, an oiefin of the formula R ¹⁷ CH=CH ₂ or R ¹⁷ CH=CHR ¹⁷ , cyclobutene, cyclopentene, substituted norbornene, or norbornene; wherein:

M is Ti, Zr, V, Cr, a rare earth metal, Co, Fe, Sc, or Ni, of Oxidation state m;

R ⁴⁴ is hydrocarbyl or substituted hydrocarbyl, and R ²³ is hydrogen, substituted hydrocarbyl or hydrocarbyl, or R ⁴⁴ and R ²⁸ taken together form a ring; R ⁴⁵ is hydrocarbyl or substituted hydrocarbyl, and R ²⁹ is hydrogen, substituted hydrocarbyl or hydrocarbyl, or R ⁴ and R ²⁹ taken together form a ring; each R is independently hydrogen, substituted hydrocarbyl or hydrocarbyl, or two of R ³⁰ taken together form a ring; n is 2 or 3; y and z are positive integers; y+z = m; each R ¹⁷ is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said oiefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms;

Q is alkyl, hydride, chloride, iodide, or bromide,-

S is alkyl, hydride, chloride, iodide, or bromide; and provided that; when norbornene or substituted norbornene is present, no other monomer is present.

Disclosed herein is a process for the production of polyolefins, comprising, contacting, at a temperature of about -100°C to about +200°C, one or more monomers selected from the group consisting of ethylene, an oiefin of the formula R ¹⁷ CH=CH ₂ or R ¹⁷ CH=CHR ¹⁷ , cyclobutene, cyclopentene, substituted

norbornene, and norbornene; optionally a source of X; with a compound of the formula

(V)

wherein:

R and R are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound directly to the imino nitrogen atom has at least two carbon atoms bound to it;

R ³ and R ⁴ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R and R ⁴ taken together are hydrocarbylene substituted hydrocarbylene to form a ring,- each R ^1' is independently hydrocarbyl or substituted hydrocarbyl provided that R ^* contains no olefinic bonds;

T is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, R ¹⁵ C(=0)- or R ^" 0C(=0)-; R ¹ is hydrocarbyl not containing olefinic or acetylenic bonds;

E is halogen or -OR ;

R ¹ is hydrocarbyl not containing olefinic or acetylenic bonds; and

X is a weakly coordinating anion; provided that, when norbornene or substituted norbornene is present, no other monomer is present. Described herein is a process for the polymerization of olefins, comprising, contacting, at a temperature of about -100°C to about +200°C: a first compound , which is a neutral Lewis acid capable cf abstracting either Q ^" or S ^~ to form WQ ^"

or WS ^" , provided that the anion formed is a weai y coordinating anion; or a cationic Lewis or Bronsted acid whose counterion is a weakly coordinating anion; a second compound of the formula

I)

and one or more monomers selected from the group consisting of ethylene, an oiefin of the formula R ^" CH=CH _: or R ¹⁷ CH=CHR ¹⁷ , 4-vinylcyclohexene, cyclobutene, cyclopentene, substituted norbornene, or norbornene,- wherein: M is Nidi), Co(II), Fe(II), or Pd(II) ;

R" and R ⁵ are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it; R ³ and R ⁴ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R and R ⁴ taken together are hydrocarbylene or substituted hydrocarbylene to form a ring; each R ¹⁷ is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said oiefin is separated from any other olefinic bond cr aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms;

Q is alkyl, hydride, chloride, iodide, or bromide,-

S is alkyl, hydride, chloride, iodide, or bromide,- and provided that;

when norbornene or substituted norbornene is present, no other monomer is present; when M is Pd a diene is not present; and except when M is Pd, when both Q and S are each independently chloride, bromide or iodide W is capable of transferring a hydride or alkyl group to M.

Included herein is a polymerization process, comprising, contacting a compound cf the formula [Pd(R ¹³ CN) ₄ ]X ₂ or a combination of Pd [OC (0) R ⁴⁰ ] ₂ and HX; a compound of the formula

(VIII)

and one or more monomers selected from the group consisting of ethylene, an oiefin of the formula R ¹ CH=CH ₂ or R ¹⁷ CH=CHR ¹⁷ , cyclopentene, cyclobutene, substituted norbornene, and norbornene; wherein:

R and R are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;

R ³ and R ⁴ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R and R ^1* taken together are hydrocarbylene or substituted hydrocarbylene to form a ring; each R ¹ is independently hydrocarbyl or substituted hydrocarbyl provided that R contains no olefinic bonds; R is hydrocarbyl;

R ^C is hydrocarbyl or substituted hydrocarbyl and

X is a weakly coordinating anion ,-

provided that, when norbornene or substituted norbornene is present, no other monomer is present.

Also described herein is a polymerization process, comprising; contacting Ni [0] , P.d[0] or Ni[I] compound containing a ligand which may be displaced by a ligand of the formula (VIII) , (XXX), (XXXII) or (XXIII); a second compound of the formula

(VIII )

(XXX)

(XXIII)

or

an oxidizing agent; a source of a relatively weakly coordinating anion,- and one or more monomers selected from the group consisting of ethylene, an oiefin of the formula R ^{1^} CH=CH ₂ or R ^" CH=CHR ^Z , cyclopentene, cyclobutene, substituted norbornene, and norbornene; wherein: R~ and R ³ are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;

R and R ⁴ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R ^" and R taken together are hydrocarbylene or substituted hydrocarbylene to form a ring; each R ^" is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said oiefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms; R ¹ is hydrocarbyl;

R ⁴ - is hydrocarbyl or substituted hydrocarbyl, and R ²⁸ is hydrogen, hydrocarbyl or substituted hydrocarbyl or R' ⁴ and R ²⁸ taken together form a ring;

R 45 is hydrocarbyl or substituted hydrocarbyl, and R' is hydrogen, substituted hydrocarbyl or hydrocarbyl or _T R^ . m and _j -R.29 taken together form a ring;

each R is independently hydrogen, substituted hydrocarbyl or hydrocarbyl, or two of R ³⁰ taken together form a ring;

R ⁴⁶ and R ⁴⁷ are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;

R ⁴⁸ and R ⁴ are each independently hydrogen, hydrocarbyl, or substituted hydrocarbyl; R and R are independently hydrocarbyl or substituted hydrocarbyl; n is 2 or 3 ;

R and R are each in independently hydrogen, hydrocarbyl or substituted hydrocarbyl; and X is a weakly coordinating anion; provided that; when norbornene or substituted norbornene is present, no other monomer is present; when said Pd[0] compound is used, a diene is not present; and when said second compound is (XXX) only an Ni[0] or Ni[I] compound is used.

Described herein is a polymerization process, comprising, contacting an Ni[0] complex containing a ligand cr ligands which may be displaced by (VIII) , oxygen, an alkyl aluminum compound, and a compound of the formula

and one or more monomers selected from the group consisting of ethylene, an oiefin of the formula

R ¹⁷ CH=CH ₂ or R ^1? CH=CHR ¹ ', cyclopentene, cyclobutene, substituted norbornene, and norbornene; wherein:

R ² and R ⁵ are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;

R and R are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R and R ⁴ taken together are hydrocarbylene or substituted hydrocarbylene to form a ring; and each R ¹ is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said oiefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms; provided that, when norbornene or substituted norbornene is present, no other monomer is present.

A polymerization process, comprising, contacting oxygen and an alkyl aluminum compound, or a compound of the formula HX, and a compound of the formula

(XXXIII)

(XXXXII) (XXXXIII)

( XXXXIV) or (XXXXV) and one or more monomers selected from the group consisting of ethylene, an oiefin of the formula R ¹⁷ CH=CH ₂ or R ¹⁷ CH=CHR ¹⁷ , cyclopentene, cyclobutene, substituted norbornene, and norbornene; wherein:

->->

R and R are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it; R ³ and R ⁴ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R and R ⁴ taken together are hydrocarbylene or substituted hydrocarbylene to form a ring; and each R ¹ is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said oiefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms;

X is a weakly coordinating anion,- and provided that, when norbornene or substituted norbornene is present, no other monomer is present.

Described herein is a polymerization process, comprising, contacting an Ni [0] complex containing a ligand or ligands which may be displaced by (VIII) , HX or a Bronsted acidic solid, and a compound of the formula

(VIII)

and one or more monomers selected from the group consisting of ethylene, an oiefin of the formula R ¹⁷ CH=CH ₂ or R ¹⁷ CH=CHR ¹⁷ , cyclopentene, cyclobutene, substituted norbornene, and norbornene; wherein:

R ² and R ⁵ are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;

R and R" are each independently yβrerg n, hydrocarbyl, substituted hydrocarbyl or R and R ⁴ taken together are hydrocarbylene or substituted hydrocarbylene to form a ring; each R ¹ is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said oiefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms; and X is a weakly coordinating anion; provided that, when norbornene or substituted norbornene is present, no other monomer is present

Described herein is a process for the polymerization of olefins, comprising, contacting, at a temperature of about -100°C to about +200°C: a first compound , which is a neutral Lewis acid capable of abstracting either Q ^" or S ^" to form WQ ^~ or WS ^" , provided that the anion formed is a weakly coordinating anion; or a cationic Lewis or Bronsted acid whose counterion is a weakly coordinating anion; a second compound of the formula

and one or more monomers selected from the group consisting of ethylene, an oiefin of the formula R ¹⁷ CH=CH ₂ or R CH=CHR ¹⁷ , cyclobutene, cyclopentene, substituted norbornene, or norbornene; wherein:

M is Ni (II) or Pd(II) ;

R ²⁰ and R ²³ are independently hydrocarbyl or substituted hydrocarbyl;

R ²¹ and R ² are each in independently hydrogen, hydrocarbyl or substituted hydrocarbyl; each R ¹⁷ is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said oiefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms; Q is alkyl, hydride, chloride, iodide, or bromide;

S is alkyl, hydride, chloride, iodide, or bromide,- and provided that; when norbornene or substituted norbornene is present, no other monomer is present; when M is Pd a diene is not present; and except when M is Pd, when both Q and S are each independently chloride, bromide or iodide W is capable of transferring a hydride or alkyl group to M.

This invention also concerns a process for the polymerization of olefins, comprising, contacting, at a temperature of about -100°C to about +200°C, a compound of the formula

(XIV)

and one or more monomers selected from the group consisting of ethylene, an oiefin of the formula R ¹⁷ CH=CH ₂ or R ¹ CH=CHR ¹⁷ , cyclopentene, cyclobutene substituted norbornene, and norbornene; wherein:

R and R ^" are each independently hycht rb i or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it; R ³ and R ⁴ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R and R ⁴ taken together are hydrocarbylene or substituted hydrocarbylene to form a ring; each R is independently hydrocarbyl or substituted hydrocarbyl provided that R contains no olefinic bonds; and each R ² is independently hydrocarbyl; each X is a weakly coordinating anion; provided that, when norbornene or substituted norbornene is present, no other monomer is present. This invention also concerns a process for the polymerization of olefins, comprising, contacting, at a temperature of about -100°C to about +200°C: a first compound , which is a neutral Lewis acid capable of abstracting either Q ^" or S ^" to form WQ ^" or WS ^~ , provided that the anion formed is a weakly coordinating anion; or a cationic Lewis or Bronsted acid whose counterion is a weakly coordinating anion; a second compound of the formula

(XV)

and one or more monomers selected from the group consisting of ethylene, an oiefin of the formula R ¹⁷ CH=CH ₂ or R ¹⁷ CH=CHR ¹⁷ , cyclopentene, cyclobutene, substituted norbornene, and norbornene; wherein:

R ⁴⁶ and R ⁴ are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;

R ⁴⁸ and R ⁴⁹ are each independently hydrogen, hydrocarbyl, or substituted hydrocarbyl; each R is independently hydrocarbyl, substituted hydrocarbyl or hydrogen;

M is Ti, Zr, Co, V, Cr, a rare earth metal, Fe, Sc , Ni, or Pd of oxidation state m; y and z are positive integers; y+z = m; each R is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said oiefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms;

Q is alkyl, hydride, chloride, iodide, or bromide;

S is alkyl, hydride, chloride, iodide, or bromide; and provided that; when norbornene or substituted norbornene is present, no other monomer is present; when M is Pd a diene is not present; and except when M is Pd, when both Q and S are each independently chloride, bromide or iodide W is capable of transferring a hydride or alkyl group to M.

Disclosed herein is a compound of the formula

(ID

wherein:

R ² and R are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;

R and R are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R and R ⁴ taken together are hydrocarbylene or substituted hydrocarbylene to form a ring; T is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, R ¹⁵ C(=0)- or R ¹⁵ OC(=0)-;

Z is a neutral Lewis base wherein the donating atom is nitrogen, sulfur or oxygen, provided that if the donating atom is nitrogen then the pKa of the conjugate acid of that compound is less than about 6; X is a weakly coordinating anion; and R is hydrocarbyl not containing olefinic or acetylenic bonds; provided that when R and R ⁴ taken together are hydrocarbylene to form a carbocyclic ring, Z is not an organic nitrile.

Described herein is a compound of the formula

wherein: R is substituted phenyl;

R ⁵¹ is phenyl or substituted phenyl; R ³ and R ⁴ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R and R taken together are hydrocarbylene or substituted hydrocarbylene to form a ring; and provided that groups in the 2 and 6 positions of R ⁵⁰ have a difference in E _s of about 0.60 or more. Described herein is a compound of the formula

R52

(XXXVI) wherein: R ⁵² is substituted phenyl;

R ^S3 is phenyl or substituted phenyl; R ³ and R ⁴ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R ³ and R ⁴ taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;

Q is alkyl, hydride, chloride, bromide or iodide;

S is alkyl, hydride, chloride, bromide or iodide; and provided that; groups in the 2 and 6 positions of R have a difference in E _s of 0.15 or more; and when both Q and S are each independently chloride, bromide or iodide W is capable of transferring a hydride or alkyl group to Ni .

This invention includes a compound of the formula

wherein:

R' and R are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom

bound to the imino nitrogen atom has at least two carbon atoms bound to it;

R and R are each independently hydrogen, hydrocarbyl, or substituted hydrocarbyl or R ³ and R ⁴ taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;

T is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, R ¹⁵ C(=0)- or R ¹⁵ OC(=0)-;

R ¹ is hydrocarbyl not containing an olefinic or acetylenic bond;

Z is a neutral Lewis acid wherein the donating atom is nitrogen, sulfur or oxygen, provided that, if the donating atom is nitrogen, then the pKa of the conjugate acid of that compound is less than about 6; and

X is a weakly coordinating anion. This invention also concerns a compound of the formula

IV)

wherein:

R ² and R ⁵ are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;

R ³ and R ⁴ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R and R ⁴ taken together are hydrocarbylene or substituted hydrocarbylene to form a ring; M is Ni (II) or Pd(II) ;

each R ¹ is independently hydrogen or alkyl containing 1 to 10 carbon atoms; n is 1, 2, or 3;

X is a weakly coordinating anion; and R ⁸ is hydrocarbyl .

Also disclosed herein is a compound of the formula

(V)

wherein:

R ² and R ⁵ are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound directly to the imino nitrogen atom has at least two carbon atoms bound to it;

R ³ and R ⁴ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R and R ⁴ taken together are hydrocarbylene or substituted hydrocarbylene to form a ring; E is halogen or -OR ¹⁸ ;

R is hydrocarbyl not containing olefinic or acetylenic bonds;

T ¹ is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, R ^1S C(=0)- or R ^1S 0C(=0)-,- R ¹⁵ is hydrocarbyl not containing olefinic or acetylenic bonds; and

X is a weakly coordinating anion. Included herein is a compound of the formula [ (η ⁴ - l^-CODJPd^Zl'X ^" , wherein-: T ¹ is hydrocarbyl not containing olefinic or acetylenic bonds;

X is a weakly coordinating anion; COD is 1, 5-cyclooctadiene;

il

Z is R CN; and

R is hydrocarbyl not containing olefinic or acetylenic bonds.

Also included herein is a compound of the formula

(VI)

wherein:

M is Ni (II) or Pd(II) ;

R and R are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound directly to the imino nitrogen atom has at least two carbon atoms bound to it;

R and R are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R and R ⁴ taken together are hydrocarbylene or substituted hydrocarbylene to form a ring; each R is independently hydrogen, alkyl or - (CH ₂ ) C0 ₂ R ¹ ,-

T is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, or -CH CH _: CH ₂ C0 ₂ R ,-

P is a divalent group containing one or more repeat units derived from the polymerization of one or more of ethylene, an oiefin of the formula R ^" CH=CH ₂ or R ¹⁷ CH=CHR ¹⁷ , cyclobutene, cyclopentene, substituted norbornene, or norbornene and, when M is Pd(II) , optionally one or more of: a compound of the formula CH ₂ =CH(CH ₂ ) _m C0 ₂ R ¹ , CO, or a vinyl ketone;

R ⁸ is hydrocarbyl; m is 0 or an integer from 1 to 16;

R ¹ is hydrogen, or hydrocarbyl or substituted hydrocarbyl containing 1 to 10 carbon atoms;

and X is a weakly coordinating anion; provided that, when M is Ni(II) , R ¹ is not -C0 ₂ R ⁸ . Also described herein is a compound of the formula

(VII)

wherein:

R ² and R ^s are each independently hydrocarbyl or 10 substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;

R ³ and R ⁴ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R and R ⁴ taken 15. together are hydrocarbylene or substituted hydrocarbylene to form a ring;

T ² is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, hydrocarbyl substituted with keto or ester groups but not containing olefinic 0 or acetylenic bonds, R ¹⁵ C(=0)- or R ¹⁵ 0C(=0)-,-

R ¹⁵ is hydrocarbyl not containing olefinic or acetylenic bonds; and

X is a weakly coordinating anion. Included herein is a process for the production of 5 polyolefins, comprising, contacting, at a temperature of about -100°C to about +200°C, a compound of the formula

(vi :

->J

and one or more monomers selected from the group consisting of ethylene, an oiefin of the formula R ¹⁷ CH=CH ₂ or R ¹⁷ CH=CHR ¹⁷ , cyclobutene, cyclopentene, substituted norbornene, and norbornene, wherein:

M is Ni (II) or Pd(ll) ;

R and R are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound directly to the imino nitrogen atom has at least two carbon atoms bound to it;

R and R are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R and R ⁴ taken together are hydrocarbylene or substituted hydrocarbylene to form a ring; each R is independently hydrogen, alkyl or - (CH ₂ ) _m C0 ₂ R ¹ ;

T is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, or -CH ₂ CH ₂ CH ₂ C0 ₂ R ⁸ ,- P is a divalent group containing one or more repeat units derived from the polymerization of one or monomers selected from the group consisting of ethylene, an oiefin of the formula R CH=CH ₂ or R ^* CH=CHR ¹⁷ , cyclopentene, cyclobutene, substituted norbornene, and norbornene, and, wnen M is Pd(II) , optionally one or more of: a compound of the formula CH ₂ =CH (CH^COzR ¹ , CO or a vinyl ketone; R is hydrocarbyl; each R ¹⁷ is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said oiefin is separated from any other olefinic bend or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms; R ¹ is hydrogen, or hydrocarbyl or substituted hydrocarbyl containing 1 to 10 carbon atoms; m is 0 or an integer of 1 to 16; and X is a weakly coordinating anion;

provided that : when M is Pd a diene is not present; when norbornene or substituted norbornene is present , no other monomer is present ,- and further provided that, when M is Ni(II) , R ¹¹ is not -C0 ₂ R ⁸ .

Included herein is a process for the production of polyolefins, comprising, contacting, at a temperature of about -100°C to about +200°C, a compound of the formula

(XVI) (X ^* )a

and one or more monomers selected from the group consisting of ethylene, an oiefin of the formula R ¹⁷ CH=CH ₂ or R ¹⁷ CH=CHR ¹⁷ , cyclobutene, cyclopentene, substituted norbornene, and norbornene, wherein: M is Zr, Ti, Sc, V, Cr, a rare earth metal, Fe,

Co, Ni or Pd of oxidation state ;

R and R are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound directly to the imino nitrogen atom has at least two carbon atoms bound to it;

R ³ and R ⁴ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R and R taken together are hydrocarbylene or substituted hydrocarbylene to form a ring; each R ^l is independently hydrogen, or alkyl, or both of R ¹¹ taken together are hydrocarbylene to form a carbocyclic ring;

33

T" is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, or -CH ₂ CH ₂ CH ₂ C0 ₂ R ;

P is a divalent group containing one or more repeat units derived from the polymerization of one or monomers selected from the group consisting of ethylene, an oiefin of the formula R CH=CH ₂ or R CH=CHR , cyclopentene, cyclobutene, substituted norbornene, and norbornene, and, when M is Pd(II) , optionally one or more of: a compound of the formula CH ₂ =CH(CH ₂ ) _m C0 ₂ R ¹ , 'CO, or a vinyl ketone; R is hydrocarbyl; a is 1 or 2; y + a + 1 = m; each R ^' is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said oiefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms; R ^" is hydrogen, or hydrocarbyl or substituted hydrocarbyl containing 1 to 10 carbon atoms,- m is 0 or an integer of 1 to 16 ,- and X is a weakly coordinating anion; provided that : when norbornene or substituted norbornene is present, no other monomer is present; when M is Pd a diene is not present; and further provided that, when M is Ni(II) , R is not -C0 ₂ R ^a . Also described herein is a compound of the formula

(XVI) (X ^"

wherein:

M is Zr, Ti, Sc, V, Cr, a rare earth metal, Fe, Co, Ni or Pd of oxidation state m; R and R are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound directly to the imino nitrogen atom has at least two carbon atoms bound to it;

R and R ⁴ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R and R ⁴ taken together are hydrocarbylene or substituted hydrocarbylene to form a ring; each R ¹¹ is independently hydrogen, or alkyl, or both of R taken together are hydrocarbylene to form a carbocyclic ring;

T is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, or -CH ₂ CH ₂ CH ₂ C0 ₂ R ⁸ ,-

P is a divalent group containing one or more repeat units derived from the polymerization of one or monomers selected from the group consisting of ethylene, an oiefin of the formula R ¹⁷ CH=CH ₂ or R ¹⁷ CH=CHR ^1? , cyclopentene, cyclobutene, substituted norbornene, and norbornene, and optionally, when M is Pd(II) , one or more of: a compound of the formula CH ₂ =CH(CH ₂ ) _r -C0 ₂ R ¹ , CO, or a vinyl ketone; Q is a monovalent anion; R ⁸ is hydrocarbyl ; a is 1 or 2; y + a + 1 = m; each R ¹⁷ is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said oiefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms; R ^* is hydrogen, or hydrocarbyl or substituted hydrocarbyl containing 1 to 10 carbon atoms; m is 0 or an integer of 1 to 16; and and X is a weakly coordinating anion;

and provided that when M is Pd a αiene is not present .

Described herein is a process, comprising, contacting, at a temperature of about -40°C to about +60°C, a compound of the formula [ (η ⁴ -l, 5-COD) PdT ^x Z] ⁺ X ^" and a diimine of the formula

(VIII:

to produce a compound of the formula

(II)

wherein:

T is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, R ¹⁵ C(=0)- or R ¹⁵ OC(=0)-,-

X is a weakly coordinating anion; COD is 1, 5-cyclooctadiene;

Z is R ¹⁰ CN;

R ^1C is hydrocarbyl not containing olefinic or acetylenic bonds;

R ¹⁵ is hydrocarbyl not containing olefinic or acetylenic bonds;

R ² and R ⁵ are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it; and

R and R are each independently yαrWgtn, hydrocarbyl, substituted hydrocarbyl or R ³ and R ⁴ taken together are hydrocarbylene or substituted hydrocarbylene to form a ring.

Described herein is a process, comprising, contacting, at a temperature of about -80°C to about +20°C, a compound of the formula (η -l, 5-COD) Pd e ₂ and a diimine of the formula

(VIII)

to produce a compound of the formula

(XXXXI)

wherein:

COD is 1, 5-cyclooctadiene;

R ² and R ⁵ are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it; and

R ³ and R ⁴ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R ³ and R ⁴ taken together are hydrocarbylene or substituted hydrocarbylene to form a ring.

Also disclosed herein is a compound of the formula

(XIV)

wherein:

R and R are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it;

R and R are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R ³ and R ⁴ taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;

15. each R is hydrocarbyl; and each X is a weakly coordinating anion. This invention includes a compound of the formula

0 :ιx)

wherei :

M is Ni (II) or Pd(II) ,-

R' and R are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound directly to the imino nitrogen atom has at least two carbon atoms bound to it;

R ^" and R ⁴ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R and R ⁴ taken

together are hydrocarbylene or substituted hydrocarbylene to form a ring; each R ¹⁴ is independently hydrogen, alkyl or R is hydrogen, or hydrocarbyl or substituted hydrocarbyl containing 1 to 10 carbon atoms;

T ⁴ is alkyl, -R ⁶⁰ C(O)OR ⁸ , R ¹⁵ (C=0) - or R ¹⁵ OC(=0)-

R is hydrocarbyl not containing olefinic or acetylenic bonds;

R is alkylene not containing olefinic or acetylenic bonds;

R is hydrocarbyl;; and X is a weakly coordinating anion; and provided that when R ¹⁴ is - (CH ₂ ) _m C0 ₂ R ¹ , or T ⁴ is not alkyl, M is Pd(II) .

Described herein is a homopolypropylene with a glass transition temperature of -30°C or less, and containing at least about 50 branches per 1000 methylene groups.

This invention also concerns a homopolymer of cyclopentene having a degree of polymerization of about 30 or more and an end of melting point of about 100°C to about 320°C, provided that said homopolymer has less than 5 mole percent of enchained linear oiefin containing pentylene units.

In addition, disclosed herein is a homopolymer or copolymer of cyclopentene that has an X-ray powder diffraction pattern that has reflections at approximately 17.3°, 19.3°, 24.2°, and 40.7° 2θ. Another novel polymer is a homopolymer of cyclopentene wherein at least 90 mole percent of enchained cyclopentylene units are 1, 3-cyclopentylene units, and said homopolymer has an average degree of polymerization of 30 more.

Described herein is a homopolymer of cyclopentene wherein at least 90 mole percent of enchained cyclopentylene units are cis-1, 3-cyclopentylene, and

said homopolymer has an average degree of polymerization of about 10 or more.

Also described is a copolymer of cyclopentene and ethylene wherein at least 75 mole percent of enchained cyclopentylene units are 1, 3-cyclopentylene units. This invention concerns a copolymer of cyclopentene and ethylene wherein there are at least 20 branches per 1000 methylene carbon atoms.

Described herein is a copolymer of cyclopentene and ethylene wherein at least 50 mole percent of the repeat units are derived from cyclopentene.

Disclosed herein is a copolymer of cyclopentene and an α-olefin.

This invention also concerns a polymerization process, comprising, contacting an oiefin of the formula R ¹⁷ CH=CH ₂ or R ¹⁷ CH=CHR ¹⁷ , wherein each R ¹⁷ is independently hydrogen, hydrocarbyl, or substituted hydrocarbyl provided that any olefinic bond in said oiefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms with a catalyst, wherein said catalyst : contains a nickel or palladium atom in a positive oxidation state; contains a neutral bidentate ligand coordinated to said nickel or palladium atom, and wherein coordination to said nickel or palladium atom is through two nitrogen atoms or a nitrogen atom and a phosphorous atom,- and said neutral bidentate ligand, has an Ethylene

Exchange Rate of less than 20,000 L-mol ^" s ^"1 when said catalyst contains a palladium atom, and less than 50,000 L-mol^s ^"1 when said catalyst contains a nickel atom; and provided that when Pd is present a diene is not present .

Described herein is a process for the polymerization of olefins, comprising, contacting, at a temperature of about -100°C to about +200°C: a first compound which is a salt of an alkali metal cation and a relatively noncoordinating monoanion; a second compound of the formula

and one or more monomers selected from the group consisting of ethylene, an oiefin of the formula R ¹⁷ CH=CH ₂ or R ¹⁷ CH=CHR ¹⁷ , cyclobutene, cyclopentene, 15. substituted norbornene, or norbornene; wherein:

R and R ⁵ are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two 0 carbon atoms bound to it;

R and R are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R and R taken together are hydrocarbylene or substituted hydrocarbylene to form a ring; 5 each R ¹⁷ is independently hydrocarbyl or substituted hydrocarbyl provided that R ¹ contains no olefinic bond;

T ¹ is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, R ¹⁵ C(=0)- or R ¹⁵ OC(=0)-; 0 S is chloride, iodide, or bromide; and provided that, when norbornene or substituted norbornene is present, no_other monomer is present.

43

Described herein is a polyolefin, comprising, a polymer made by polymerizing one or more monomers of the formula H ₂ C=CH(CH ₂ ) _e G by contacting said monomers with a transition metal containing coordination polymerization catalyst, wherein: each G is independently hydrogen or -C0R ¹ ; each e is independently 0 or an integer of 1 to 20; each R ^* is independently hydrogen, hydrocarbyl or substituted hydrocarbyl; and provided that : said polymer has at least 50 branches per 1000 methylene groups; in at least 50 mole percent of said monomers G is hydrogen; and except when no branches should be theoretically present, the number of branches per 1000 methylene groups is 90% or less than the number of theoretical branches per 1000 methylene groups, or the number of branches per 1000 methylene groups is 110% or more of theoretical branches per 1000 methylene groups, and when there should be no branches theoretically present, said polyolefin has 50 or more branches per 1000 methylene groups; and provided that said polyolefin has at least two branches of different lengths containing less than 6 carbon atoms each.

Also described herein is a polyolefin, comprising, a polymer made by polymerizing one or more monomers of the formula H ₂ C=CH(CH ₂ ) _e G by contacting said monomers with a transition metal containing coordination polymerization catalyst, wherein: each G is independently hydrogen cr -CC^R ¹ ,- each e is independently 0 or an integer of 1 to 20;

R ¹ is independently hydrogen, hydrocarbyl or substituted hydrocarbyl; and provided tha :

said polymer has at least 50 branches per 1000 methylene groups; in at least 50 mole percent of said monomers G is hydrogen; said polymer has at least 50 branches of the formula -(CH ₂ ) _f G per 1000 methylene groups, wherein when G is the same as in a monomer and e≠f , and/or for any single monomer of the formula H ₂ C=CH(CH ₂ ) _e G there are less than 90% of the number of theoretical branches per 1000 methylene groups, or more than 110% of the theoretical branches per 1000 methylene groups of the formula -(CH ₂ ) _f G and f=e, and wherein f is 0 or an integer of 1 or more; and provided that said polyolefin has at least two branches of different lengths containing less than 6 carbon atoms.

This invention concerns a process for the formation of linear α-olefins, comprising, contacting, at a temperature of about -100°C to about +200°C: ethylene; a first compound W, which is a neutral Lewis acid capable of abstracting X ^" to form WX ^" , provided that the anion formed is a weakly coordinating anion, or a cationic Lewis or Bronsted acid whose counterion is a weakly coordinating anion; and a second compound of the formula

R2

(XXXI) wherein: R ² and R ⁵ are each independently hydrocarbyl or substituted hydrocarbyl;

R ³ and R ⁴ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R ³ and R ⁴ taken

together are hydrocarbylene or substituted hydrocarbylene to form a ring; and

Q and S are each independently chlorine, bromine, iodine or alkyl; and wherein an α-olefin containing 4 to 40 carbon atoms is produced.

This invention also concerns a process for the formation of linear α-olefins, comprising, contacting, at a temperature of about -100°C to about +200°C: ethylene and a compound of the formula

:ιιi) or

(XXXIV)

wherein: R and R are each independently hydrocarbyl or substituted hydrocarbyl;

R ³ and R ⁴ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R and R ⁴ taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;

T ¹ is hydrogen or n-alkyl containing up to 38 carbon atoms;

Z is a neutral Lewis base wherein the donating atom is nitrogen, sulfur, or oxygen, provided that if

the donating atom is nitrogen then the pKa of the conjugate acid of that compound (measured in water) is less than about 6;

U is n-alkyl containing up to 38 carbon atoms; and

X is a noncoordinating anion; and wherein an α-olefin containing 4 to 40 carbon atoms is produced.

Another novel process is a process for the formation of linear α-olefins, comprising, contacting, at a temperature of about -100°C to about +200°C: ethylene; and a Ni[II] of

R and R are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it; R ³ and R ⁴ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R and R ⁴ taken together are hydrocarbylene substituted hydrocarbylene to form a carbocyclic ring and wherein an α-olefin containing 4 to 40 carbon atoms is produced.

Also described herein is a process for the production of polyolefins, comprising, contacting, at a temperature of about 0°C to about +200°C, a compound of the formula

and one or more monomers selected from the group consisting of ethylene, an oiefin of the formula R ¹⁷ CH=CH ₂ or R ¹ 'CH=CHR ¹⁷ , cyclobutene, cyclopentene, substituted norbornene, and norbornene, wherein:

M is Ni (II) or Pd(II) ,- A is a π-allyl or π-benzyl group; R ^~ and R ^' are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound directly to the imino nitrogen atom has at least two carbon atoms bound to it;

R and R ⁴ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R ^" and R ⁴ taken together are hydrocarbylene or substituted hydrocarbylene to form a ring; each R is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said oiefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms; and X is a weakly coordinating anion; and provided that : when M is Pd a diene is not present; and when norbornene or substituted norbornene is present, no other monomer is present.

The invention also includes a compound of the formula

\ M /

R ⁴

XXXVII wherein :

M is Ni(II) or Pd(II) ; A is a π-allyl or π-benzyl group; R ² and R ⁵ are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound directly to the imino nitrogen atom has at least two carbon atoms bound to it;

R and R ⁴ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R ^J and R ^"* taken together are hydrocarbylene or substituted hydrocarbylene to form a ring; each R ¹⁷ is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said oiefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms; and X is a weakly coordinating anion; and provided that when M is Pd a diene is not present.

This invention also includes a compound of the formula

wherein:

R and R ^* are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R and R ⁴ taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;

R ⁴ is hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound directly to the imino nitrogen atom has at least two carbon atoms bound to it; each R is independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or a functional group,-

W is alkylene or substituted alkylene containing 2 or more carbon atoms;

Z is a neutral Lewis base wherein the donating atom is nitrogen, sulfur, or oxygen, provided that if the donating atom is nitrogen then the pKa of the conjugate acid of that compound (measured in water) is less than about 6, or an oiefin of the formula R ¹⁷ CH=CHR ¹⁷ ; each R is independently hydrogen, saturated hydrocarbyl or substituted saturated hydrocarbyl; and X is a weakly coordinating anion; and provided that when M is Ni, W is alkylene and each R ' is independently hydrogen or saturated hydrocarbyl .

This invention also includes a process for the production of a compound of the formula

(XXXVIII)

comprising, heating a compound of the formula

(XXXIX) at a temperature of about -30°C to about +100° for a sufficient time to produce (XXXVIII) , and wherein: R and R ⁴ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R ^" and R ⁴ taken - together are hydrocarbylene or substituted hydrocarbylene to form a ring; R ⁵⁴ is hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound directly to the imino nitrogen atom has at least two carbon atoms bound to it; each R is independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or a functional group,-

R is alkyl containing 2 to 30 carbon atoms; T ⁵ is alkyl;

W is alkylene containing 2 to 30 carbon atoms; Z is a neutral Lewis base wherein the donating atom is nitrogen, sulfur, or oxygen, provided that if the donating atom is nitrogen then the pKa of the conjugate acid of that compound (measured in water) is less than about 6; and X is a weakly coordinating anion.

This invention also concerns a process for the polymerization of olefins, comprising, contacting a compound of the formula

(XXXVIII) and one or more monomers selected from the group consisting of ethylene, an oiefin of the formula R ^" CH=CH ₂ or R ¹⁷ CH=CHR ¹⁷ , cyclobutene, cyclopentene, substituted norbornene, and norbornene, wherein:

R and R are each independently hydrogen, ydrocarbyl, substituted hydrocarbyl or R and R ⁴ taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;

R ⁴ is hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound directly to the imino nitrogen atom has at least two carbon atoms bound to it; each R is independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or a functional group;

W is alkylene or substituted alkylene containing 2 or more carbon atoms; Z is a neutral Lewis base wherein the donating atom is nitrogen, sulfur, or oxygen, provided that f the donating atom is nitrogen then the pKa of the conjugate acid of that compound (measured in water) is less than about 6, or an oiefin of the formula each R ¹ is independently hydrogen, saturated hydrocarbyl or substituted saturated hydrocarbyl; and X is a weakly coordinating anion; and provided that : when M is Ni, W is alkylene and each R ¹ ' is independently hydrogen or saturated hydrocarbyl;

and when norbornene or substituted norbornene is present, no other monomer is present.

This invention also concerns a homopolypropylene containing about 10 to about 700 δ+ methylene groups per 1000 total methylene groups in said homopolypropylene.

Described herein is a homopolypropylene wherein the ratio of δ+:γ methylene groups is about 0.5 to about 7. Also included herein is a homopolypropylene in which about 30 to about 85 mole percent of the monomer units are enchained in an ω,l fashion.

DETAILS OF THF, INVENTION Herein certain terms are used to define certain chemical groups or compounds. These terms are defined below.

• A "hydrocarbyl group" is a univalent group containing only carbon and hydrogen. If not otherwise stated, it is preferred that hydrocarbyl groups herein contain 1 to about 30 carbon atoms.

• By "not containing olefinic or acetylenic bonds" is meant the grouping does not contain olefinic carbon-carbon double bonds (but aromatic rings are not excluded) and carbon-carbon triple bonds. • By "substituted hydrocarbyl" herein is meant a hydrocarbyl group which contains one or more substituent groups which are inert under the process conditions to which the compound containing these groups is subjected. The substituent groups also do not substantially interfere with the process. If not otherwise stated, it is preferred that substituted hydrocarbyl groups herein contain 1 to about 30 carbon atoms. Included in the meaning of "substituted" are heteroaromatic rings. • By an alkyl aluminum compound is meant a compound in which at least one alkyl group is bound to an aluminum atom. Other groups such as alkoxide,

oxygen, and halogen may also be bound to aluminum atoms in the compound.

• By "hydrocarbylene" herein is meant a divalent group containing only carbon and hydrogen. Typical hydrocarbylene groups are - (CH ₂ ) ₄ -, - CH ₂ CH(CH ₂ CH ₃ )CH ₂ CH ₂ - and

(An)

If not otherwise stated, it is preferred that hydrocarbylene groups herein contain 1 to about 30 carbon atoms .

• By "substituted hydrocarbylene" herein is meant a hydrocarbylene group which contains one or more substituent groups which are inert under the process conditions to which the compound containing these groups is subjected. The substituent groups also do not substantially interfere with the process. If not otherwise stated, it is preferred that substituted hydrocarbylene groups herein contain 1 to about 30 carbon atoms. Included within the meaning of "substituted" are heteroaromatic rings.

• By substituted norbornene is meant a norbornene which is substituted with one cr more groups which does not interfere substantially with the polymerization. It is preferred that substituent groups (if they contain carbon atoms) contain 1 to 30 carbon atoms. Examples of substituted norbornenes are ethyiidene norbornene and methylene norbornene.

• By "saturated hydrocarbyl" is meant a univalent group containing only carbon and hydrogen which contains no unsaturation, such as olefinic, acetylenic, or aromatic groups. Examples of such groups include alkyl and cycloalkyl . If not otherwise

stated, it is preferred that saturated hydrocarbyl groups herein contain 1 to about 30 carbon atoms.

• By "neutral Lewis base" is meant a compound, which is not an ion, which can act as a Lewis base. Examples of such compounds include ethers, amines, sulfides, and organic nitriles.

• By "cationic Lewis acid" is meant a cation which can act as a Lewis acid. Examples of such cations are sodium and silver cations. • By "α-olefin" is meant a compound of the formula CH ₂ =CHR , wherein R is n-alkyl or branched alkyl, preferably n-alkyl.

• By "linear α-olefin" is meant a compound of the formula CH ₂ =CHR ¹⁹ , wherein R ¹⁹ is n-alkyl. It is preferred that the linear α-olefin have 4 to 40 carbon atoms.

• By a "saturated carbon atom" is meant a carbon atom which is bonded to other atoms by single bonds only. Not included in saturated carbon atoms are carbon atoms which are part of aromatic rings.

• By a quaternary carbon atom is meant a saturated carbon atom which is not bound to any hydrogen atoms. A preferred quaternary carbon atom is bound to four other carbon atoms. • By an olefinic bond is meant a carbon-carbon double bond, but does not include bonds in aromatic rings .

• By a rare earth metal is meant one of lanthanum, cerium, praeseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium or lutetium.

This invention concerns processes for making polymers, comprising, contacting one or more selected olefins or cycloolefins, and optionally an ester or carboxylic acid of the formula CH ₂ =CH(CH ₂ ) _m C0 ₂ R ¹ , and other selected monomers, with a transition metal containing catalyst (and possibly other catalyst

components) . Such catalysts are, for instance, various complexes of a diimine with these metals. By a "polymerization process herein (and the polymers made therein) " is meant a process which produces a polymer with a degree of polymerization (DP) of about 20 or more, preferably about 40 or more [except where otherwise noted, as in P in compound (VI)] By "DP" is meant the average number of repeat (monomer) units in the polymer.

One of these catalysts may generally be written as

(I)

wherein: M is Ni(II) , Co (II) , Fe (11) or Pd(II) ; R and R are each independently hydrocarbyl or substituted hydrocarbyl , provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it; R and R ⁴ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R and R ⁴ taken together are hydrocarbylene or substituted hydrocarbylene to form a ring; Q is alkyl, hydride, chloride, iodide, or bromide; and S is alkyl, hydride, chloride, iodide, or bromide. Preferably M is Ni(II) or Pd(II) .

In a preferred form of (I) , R ³ and R ⁴ are each independently hydrogen or hydrocarbyl . If Q and/or S is alkyl, it is preferred that the alkyl contains 1 to 4 carbon atoms, and more preferably is methyl. Another useful catalyst is

(ID

wherein: R and R ⁵ are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it; R • and R ⁴ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R and R ⁴ taken together are hydrocarbylene or substituted hydrocarbylene to form a ring; T ¹ is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, R ^1S C(=0)- or R ¹⁵ OC(=0)-; Z is a neutral Lewis base wherein the donating atom is nitrogen, sulfur or oxygen, provided that, if the donating atom is nitrogen, then the pKa of the conjugate acid of that compound is less than about 6; X is a weakly coordinating anion; and R is hydrocarbyl not containing olefinic or acetylenic bonds.

In one preferred form of (II) , R ³ and R ⁴ are each independently hydrogen or hydrocarbyl. In a more preferred form of (II) , T ¹ is alkyl, and T ¹ is especially preferably methyl. It is preferred that Z is R ⁶ ₂ 0 or R ⁷ CN, wherein each R ⁶ is independently hydrocarbyl and R' is hydrocarbyl. It is preferred that R ⁶ and R' are alkyl, and it is more preferred that they are methyl or ethyl. It is preferred that X ^" is BAF, SbF ₆ , PF _€ or BF ₄ .

Another useful catalyst is

III)

wherein: R 2 and R5 are each independently hydrocarbyl 5 or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it; R ³ and R ⁴ are each independently hydrogen, hydrocarbyl, or substituted hydrocarbylene, or R and R taken together are

10 hydrocarbylene or substituted hydrocarbylene to form a ring; T is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, R ¹⁵ C(=0)- or R ^~= 0C (=0) - ; Z is a neutral Lewis base wherein the donating atom is nitrogen, sulfur or oxygen, provided that if the

15. donating atom is nitrogen then the pKa of the conjugate acid of that compound is less than about 6; X is a weakly coordinating anion; and R ¹⁵ is hydrocarbyl not containing olefinic or acetylenic bonds.

In one preferred form of (III) , R and R ^"* are each 0 independently hydrogen, hydrocarbyl. In a more preferred form of (III) T ¹ is alkyl, and T ^* is especially preferably methyl . It is preferred that Z is R ₂ 0 or R CN, wherein each R is independently hydrocarbyl and R ⁷ is hydrocarbyl. It is preferred 5 that R ⁶ and R are alkyl, and it is especially preferred that they are methyl or ethyl. It is preferred that X ^" is BAF ^~ , SbF _€ ', PF _€ " or BF ₄ ".

Relatively weakly coordinating anions are known to the artisan. Such anions are often bulky anions, 0 particularly those that may delocalize their negative charge. Suita'ble weakly coordinating anions in this Application include (Ph) ₄ B ^" (Ph = phenyl) , tetrakis [3 , 5-bis (trifluoromethyl) phenyl] borate (herein

abbreviated BAF) , PF ₆ ^" , BF ₄ ^" , SbF ₆ ^" , trifluoromethanesulfonate, p-toluenesulfonate, (R _f S0 ₂ ) ₂ N ^" , and (C ₆ F ₅ ) ₄ B ^~ . Preferred weakly coordinating anions include BAF ^" , PF ₆ ^" , BF ₄ ^" , and SbF ₆ ^" .

Also useful as a polymerization catalyst is a compound of the formula

(IV)

wherein: R ² and R ⁵ are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it; R ³ and R ⁴ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R ³ and R ⁴ taken together are hydrocarbylene or substituted hydrocarbylene to form a ring; M is Ni(II) or Pd(II) ; each R ¹⁶ is independently hydrogen or alkyl containing 1 to 10 carbon atoms; n is 1, 2, or 3; X is a weakly coordinating anion; and R is hydrocarbyl .

It is preferred that n is 3, and all of R ¹⁶ are hydrogen. It is also preferred that R ⁸ is alkyl or substituted alkyl, especially preferred that it is alkyl, and more preferred that R is methyl.

Another useful catalyst is

(V)

wherein: R ² and R ⁵ are hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound directly to the imino nitrogen atom has at least two carbon atoms bound to it; R ³ and R ⁴ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R and R ⁴ taken together are hydrocarbylene or substituted hydrocarbylene to form a ring; T is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, R ¹⁵ C(=0)- or R ¹⁵ OC(=0)-; R ^* is hydrocarbyl not containing olefinic or acetylenic bonds; E is halogen or -OR ; R is hydrocarbyl not containing olefinic or acetylenic bonds; and X is a weakly coordinating anion. It is preferred that T ¹ is alkyl containing 1 to 4 carbon atoms, and more preferred that it is methyl. In other preferred compounds (V) , R ³ and R ⁴ are methyl or hydrogen and R ² and R ⁵ are 2, 6-diisopropylphenyl and X is BAF. It is also preferred that E is chlorine. Another useful catalyst is a compound of the formula

(VII;

wherein: R ^* and R are each independently hydrocarbyl or substituted hydrocarbyl , provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it; R ³ and R ⁴ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R and R ⁴ taken together are hydrocarbylene or substituted hydrocarbylene to form a

ring; T is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, hydrocarbyl substituted with keto or ester groups but not containing olefinic or acetylenic bonds, R ¹⁵ C(=0)- or R ¹⁵ OC(=0)-; R ¹⁵ is hydrocarbyl not containing olefinic or acetylenic bonds; and X is a weakly coordinating anion. In a more preferred form of (VII) , T ² is alkyl containing 1 to 4 carbon atoms and T is especially preferably methyl. It is preferred that X is perfluoroalkylsulfonate, especially trifluoromethanesulfonate (triflate) . If X ^" is an extremely weakly coordinating anion such as BAF, (VII) may not form. Thus it may be said that (VII) forms usually with weakly, but perhaps not extremely weakly, coordinating anions. In all compounds, intermediates, catalysts, processes, etc. in which they appear it is preferred that R~ and R are each independently hydrocarbyl, and in one form it is especially preferred that R and R are both 2, 6-diisopropylphenyl, particularly when R ³ and R are each independently hydrogen or methyl . It is also preferred that R and R ⁴ are each independently hydrogen, hydrocarbyl or taken together hydrocarbylene to form a carbocyclic ring.

Compounds of the formula (I) wherein M is Pd, Q is alkyl and S is halogen may be made by the reaction of the corresponding 1, 5-cyclooctadiene (COD) Pd complex with the appropriate diimine. When M is Ni, I) can be made by the displacement of a another ligand, such as a dialkylether or a polyether such as 1,2- dimethoxyethane, by an appropriate diimine.

Catalysts of formula (II) , wherein X ^" is BAF ^" , may be made by reacting a compound of formula (I) wherein Q is alkyl and S is halogen, with about one equivalent of an alkali metal salt, particularly the sodium salt, of HBAF, in the presence of a coordinating ligand, particularly a nitrile such as acetonitrile. When X ^" is an anion such as BAF ^" , SbF ₆ ^" or BF ₄ ^' the same

starting palladium compound can be reacted with the silver salt AgX.

However, sometimes the reaction of a diimine with a 1, 5-COD Pd complex as described above to make compounds of formula (II) may be slow and/or give poor conversions, thereby rendering it difficult to make the starting material for (II) using the method described in the preceding paragraph. For instance when: R ² =R ⁵ =Ph ₂ CH- and R ³ =R ⁴ =H; R ² =R ⁵ =Ph- and R ³ =R ⁴ =Ph; R ² =R ⁵ =2- t-butylphenyl and R ³ =R =CH ₃ ; R ² =R ⁵ =α-naphthyl and R ³ =R =CH ₃ ; and R =R ⁵ =2-phenylphenyl and R ³ =R ⁴ =CH ₃ difficulty may be encountered in making a compound of formula (II) .

In these instances it has been found more convenient to prepare (II) by reacting [(η ⁴ -l,5-

COD) PdT ^x Z] ⁺ X ^" , wherein T ¹ and X are as defined above and Z is an organic nitrile ligand, preferably in an organic nitrile solvent, with a diimine of the formula

(VIII)

By a "nitrile solvent" is meant a solvent that is at least 20 volume percent nitrile compound. The product of this reaction is (II) , in which the Z ligand is the nitrile used in the synthesis. In a preferred synthesis, T ¹ is methyl and the nitrile used is the same as in the starting palladium compound, and is more preferably acetonitrile . The process is carried out in solution, preferably when the nitrile is substantially all of the solvent, at a temperature of about -40°C to about +60°C, preferably about 0°C to about 30°C. It is

preferred that the reactants be used in substantially equimolar quantities.

The compound [ (η -l, 5-COD) PdT ^x Z] ⁺ X ^" , wherein T ¹ is alkyl, Z is an organic nitrile and X is a weakly coordinating anion may be made by the reaction of [ (η ⁴ - 1, 5-COD) PdT ^x A, wherein A is Cl, Br or I and T ¹ is alkyl with the silver salt of X ^" , AgX, or if X is BAF with an alkali metal salt of HBAF, in the presence of an organic nitrile, which of course will become the ligand T ¹ . In a preferred process A is Cl, T ¹ is alkyl, more preferably methyl, and the organic nitrile is an alkyl nitrile, more preferably acetonitrile. The starting materials are preferably present in approximately equimolar amounts, except for the nitrile which is present preferably in excess. The solvent is preferably a non-coordinating solvent such as a halocarbon. Methylene chloride is useful as such a solvent . The process preferably is carried out at a temperature of about -40°C to about +50°C. It is preferred to exclude water and other hydroxyl containing compounds from the process, and this may be done by purification of the ingredients and keeping the process mass under an inert gas such as nitrogen.

Compounds of formula (II) [or (III) when the metal is nickel] can also be made by the reaction of

with a source of the conjugate acid of the anion X, the acid HX or its equivalent (such as a trityl salt) in the presence of a solvent which is a weakly coordinating ligand such as a dialkyl ether or an alkyl

nitrile. It is preferred to carry out this reaction at about -80°C to about 30°C.

Compounds of formula (XXXXI) can be made by a process, comprising, contacting, at a temperature of about -80°C to about +20°C, a compound of the formula ( η ⁴ -l, 5-COD) PdMe ₂ and a diimine of the formula

(VIII)

wherein: COD is 1, 5-cyclooctadiene; R ^* and R ⁵ are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it; and R and R are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R and R ⁴ taken together are hydrocarbylene or substituted hydrocarbylene to form a ring. It is preferred that the temperature is about -50°C to about +10°C. It is also preferred that the two starting materials be used in approximately equimolar quantities, and/or that the reaction be carried out in solution. It is preferred that R ² and R ^s are both 2-t-butylphenyl or 2,5-di-t- butylphenyl and that R ³ and R ⁴ taken together are An, or R ³ and R ⁴ are both hydrogen or methyl .

Compounds of formula (IV) can be made by several routes. In one method a compound of formula (II) is reacted with an acrylate ester of the formula CH ₂ =CHC0 ₂ R ¹ wherein R ¹ is as defined above. This reaction is carried out in a non-coordinating solvent such as methylene chloride, preferably using a greater than 1 to 50 fold excess of the acrylate ester. In a

preferred reaction, Q is methyl, and R~ is alkyl containing 1 to 4 carbon atoms, more preferably methyl. The process is carried out at a temperature of about - 100°C to about +100°C, preferably about 0°C to about 50°C. It is preferred to exclude water and other hydroxyl containing compounds from the process, and this may be done by purification of the ingredients and keeping the process mass under an inert gas such as nitrogen Alternatively, (IV) may be prepared by reacting (I), wherein Q is alkyl and S is Cl, Br or I with a source of an appropriate weakly coordinating anion such as AgX or an alkali metal salt of BAF and an acrylate ester (formula as immediately above) in a single step.. Approximately equimolar quantities of (I) and the weakly coordinating anion source are preferred, but the acrylate ester may be present in greater than 1 to 50 fold excess. In a preferred reaction, Q is methyl, and R ¹ is alkyl containing 1 to 4 carbon atoms, more preferably methyl. The process is preferably carried out at a temperature of about -100°C to about +100°C, preferably about 0°C to about 50°C. It is preferred to exclude water and other hydroxyl containing compounds from the process, and this may be done by purification of the ingredients and keeping the process mass under an inert gas such as nitrogen.

In another variation of the preparation of (IV) from (I) the source of the weakly coordinating anion is a compound which itself does not contain an anion, but which can combine with S [of (I)] to form such a weakly coordinating anion. Thus in this type of process by "source of weakly coordinating anion" is meant a compound which itself contains the anion which will become X ^" , or a compound which during the process can combine with other process ingredients to form such an anion.

Catalysts of formula (V) , wherein X ^" is BAF ^" , may be made by reacting a compound of formula (I) wherein Q

is alkyl and S is halogen, with about one- alt 01 an equivalent of an alkali metal salt, particularly the sodium salt, of HBAF. Alternatively, (V) containing other anions may be prepared by reacting (I) , wherein Q is alkyl and S is Cl, Br or I with one-half eσuivalent of a source of an appropriate weakly coordinating anion such as AgX.

Some of the nickel and palladium compounds described above are useful in processes for polymerizing various olefins, and optionally also copolymerizing olefinic esters, carboxylic acids, or other functional olefins, with these olefins. When (I) is used as a catalyst, a neutral Lewis acid or a cationic Lewis or Bronsted acid whose counterion is a weakly coordinating anion is also present as part of the catalyst system (sometimes called a "first compound" in the claims) . By a "neutral Lewis acid" is meant a compound which is a Lewis acid capable for abstracting Q ^" or S ^" from (I) to form a weakly coordination anion. The neutral Lewis acid is originally uncharged (i.e., not ionic) . Suitable neutral Lewis acids include SbF ₅ , Ar ₃ B (wherein Ar is aryl) , and BF ₃ . By a cationic Lewis acid is meant a cation with a positive charge such as Ag ⁺ , K ^* , and Na ⁺ . In those instances in which (I) (and similar catalysts which require the presence of a neutral Lewis acid or a cationic Lewis or Bronsted acid) , does not contain an alkyl or hydride group already bonded to the metal (i.e., neither Q or S is alkyl or hydride) , the neutral Lewis acid or a cationic Lewis or Bronsted acid also alkylates or adds a hydride to the metal, i.e., causes an alkyl group or hydride to become bonded to the metal atom.

A preferred neutral Lewis acid, which can alkylate the metal, is a selected alkyl aluminum compound, such as R ⁹ ₃ A1, R ⁵ _: A1C1, R ⁹ AlCl ₂ , and "R ⁹ AlO"

(alkylalummoxanes) , wherein R ⁹ is alkyl containing 1 to 25 carbcn atoms, preferably 1 to 4 carbon atoms.

Suitable alkyl aluminum compounds include methylaluminoxane (which is an oligomer with the general formula [MeA10]„), (C ₂ H ₅ ) ₂ A1C1, C ₂ H ₅ A1C1 ₂ , and [ (CH ₃ ) ₂ CHCH ₂ ] ₃ A1. Metal hydrides such as NaBH ₄ may be used to bond hydride groups to the metal M.

The first compound and (I) are contacted, usually in the liquid phase, and in the presence of the oiefin, and/or 4-vinylcyclohexene, cyclopentene, cyclobutene, substituted norbornene, or norbornene. The liquid phase may include a compound added just as a solvent and/or may include the monomer(s) itself. The molar ratio of first compound:nickel or palladium complex is about 5 to about 1000, preferably about 10 to about 100. The temperature at which the polymerization is carried out is about -100°C to about +200°C, preferably about -20°C to about +80°C. The pressure at which the polymerization is carried out is not critical, atmospheric pressure to about 275 MPa, or more, being a suitable range. The pressure may affect the microstructure of the polyolefin produced (see below) .

When using (I) as a catalyst, it is preferred that R ³ and R ⁴ are hydrogen, methyl, or taken together are

(An)

It is also preferred that both R ² and R ^ε are 2,6- diisopropylphenyl, 2, 6-dimethylphenyl, 2,6- diethylphenyl, 4-methylphenyl, phenyl, 2,4,6- trimethylphenyl, and 2-t-butylphenyl . When M is Ni(II), it is preferred that Q and S are each independently chloride or bromide, while when M is Pd(II) it is preferred that Q is methyl, chloride, or bromide, and S is chloride, bromide or methyl. In

addition, the specific combinations of groups" m ^' he- catalysts listed in Table I are especially preferred.

Table I

M

Note - In Tables I and II, and elsewhere herein, the following convention and abbreviations are used. For R ² and R ⁵ , when a substituted phenyl ring is present, the amount of substitution is indicated by the number of numbers indicating positions on the phenyl

ring, so that, for example, 2,6-i-PrPh is 2,6- diisopropylphenyl. The following abbreviations are used: i-Pr = isopropyl; Me = methyl; Et = ethyl; t-Bu = t-butyl; Ph = phenyl; Np = naphthyl; An = 1,8- naphthylylene (a divalent radical used for both R ³ and R ⁴ , wherein R ³ and R ⁴ taken together form a ring, which is part of an acenaphthylene group) ; OTf = triflate; and BAF = tetrakis [3, 5- bis (trifluoromethyl)phenyl]borate.

Preferred olefins in the polymerization are one or more of ethylene, propylene, 1-butene, 2-butene, 1- hexene l-octene, 1-pentene, 1-tetradecene, norbornene, and cyclopentene, with ethylene, propylene and cyclopentene being more preferred. Ethylene (alone as a homopolymer) is especially preferred.

The polymerizations with (I) may be run in the presence of various liquids, particularly aprotic organic liquids. The catalyst system, monomer(s) , and polymer may be soluble or insoluble in these liquids, but obviously these liquids should not prevent the polymerization from occurring. Suitable liquids include alkanes, cycloalkanes, selected halogenated hydrocarbons, and aromatic hydrocarbons. Specific useful solvents include hexane, toluene and benzene. Whether such a liquid is used, and which and how much liquid is used, may affect the product obtained. It may affect the yield, microstructure, molecular weight, etc., of the polymer obtained. Compounds of formulas (XI), (XIII) , (XV) and (XIX) may also be used as catalysts for the polymerization of the same monomers as compounds of formula (I) . The polymerization conditions are the same for (XI) , (XIII) , (XV) and (XIX) as for (I), and the same Lewis and Bronsted acids are used as co-catalysts. Preferred groupings R ² , R ³ , R ⁴ , and R ⁵ (when present) in (XI) and (XIII) are the same as in (I) , both in a polymerization process and as compounds in their own right .

Preferred (XI) compounds have the metals Sc(III) , Zr(IV) , Ni(II) , Ni(I) , Pd(II) , Fe(II) , and Co(II) . When M is Zr, Ti, Fe, and Sc it is preferred that all of Q and S are chlorine or bromine more preferably chlorine. When M is Ni or Co it is preferred that all of Q and S are chlorine, bromine or iodine, more preferably bromine.

In (XVII) preferred metals are Ni(II) and Ti(IV) . It is preferred that all of Q and S are halogen. It is also preferred that all of R ²⁸ , R ²⁹ , and R ³⁰ are hydrogen, and/or that both R ⁴ and R ⁴ are 2,4,6- trimethylphenyl or 9-anthracenyl .

In (XV) it is preferred that both of R ^' are hydrogen. In (XIII) , (XXIII) and (XXXII) (as polymerization catalysts and as novel compounds) it is preferred that all of R ²⁰ , R ²¹ , R ²² and R ²³ are methyl. It is also preferred that T ¹ and T ² are methyl. For (XIII) , when M is Ni(I) or (II), it is preferred that both Q and S are bromine, while when M is Pd it is preferred that Q is methyl and S is chlorine.

Compounds (II) , (IV) or (VII) will each also cause the polymerization of one or more of an oiefin, and/or a selected cyclic oiefin such as cyclobutene, cyclopentene or norbornene, and, when it is a Pd(II) complex, optionally copolymerize an ester or carboxylic acid of the formula CH ₂ =CH (CH ₂ ) _m C0 ₂ R~, wherein m is 0 or an integer of 1 to 16 and R ¹ is hydrogen or hydrocarbyl or substituted hydrocarbyl, by themselves (without cocatalysts) . However, (III) often cannot be used when the ester is present. When norbornene or substituted norbornene is present no other monomer should be present .

Other monomers which may be used with compounds (II) , (IV) or (VII) (when it is a Pd(II) complex) to form copolymers with olefins and selected cycloolefins are carbon monoxide (CO) , and vinyl ketones of the general formula H ₂ C=CHC (O) R ²⁵ , wherein R ²⁵ is alkyl

containing 1 to 20 carbon atoms, and it is preferred that R is methyl. In the case of the vinyl ketones, the same compositional limits on the polymers produced apply as for the carboxylic acids and esters described as comonomers in the immediately preceding paragraph. CO forms alternating copolymers with the various olefins and cycloolefins which may be polymerized with compounds (II) , (IV) or (VII) . The polymerization to form the alternating copolymers is done with both CO and the oiefin simultaneously in the process mixture, and available to the catalyst. It is also possible to form block copolymers containing the alternating CO/ (cyclo) olefin copolymers and other blocks containing just that oiefin or other olefins or mixtures thereof. This may be done simply by sequentially exposing compounds (II), (IV) or (VII), and their subsequent living polymers, to the appropriate monomer or mixture of monomers to form the desired blocks. Copolymers of CO, a (cyclo) olefin and a saturated carboxylic acid or ester of the formula CH ₂ =CH(CH ₂ ) _m C0 ₂ R ¹ , wherein m is 0 or an integer of 1 to 16 and R ¹ is hydrogen or hydrocarbyl or substituted hydrocarbyl, may also be made by simultaneously exposing the polymerization catalyst or living polymer to these 3 types of monomers.

The polymerizations may be carried out with (II) , (III) , (IV) or (VII) , and other catalyst molecules or combinations, initially in the solid state [assuming (II) , (III) (IV) or (VII) is a solid] or in solution. The oiefin and/or cycloolefin may be in the gas or liquid state (including gas dissolved in a solvent) . A liquid, which may or may not be a solvent for any or all of the reactants and/or products may also be present. Suitable liquids include alkanes, cycloalkanes, halogenated alkanes and cycloalkanes, ethers, water, and alcohols, except that when (III) is used, hydrocarbons should preferably be used as solvents. Specific useful solvents include methylene

chloride, hexane, C0 ₂ , chloroform, perfluorδ ^" (n- butyltetrahydrofuran) (herein sometimes called FC-75) , toluene, dichlorobenzene, 2-ethylhexanol, and benzene. It is particularly noteworthy that one of the liquids which can be used in this polymerization process with (II) , (III) , (IV) or (VII) is water, see for instance Examples 213-216. Not only can water be present but the polymerization "medium" may be largely water, and various types of surfactants may be employed so that an emulsion polymerization may be done, along with a suspension polymerization when surfactants are not employed.

Preferred olefins and cycloolefins in the polymerization using (II) , (III) or (IV) are one or more of ethylene, propylene, l-butene, 1-hexene, 1- octene, l-butene, cyclopentene, 1-tetradecene, and norbornene; and ethylene, propylene and cyclopentene are more preferred. Ethylene alone is especially preferred. Olefinic esters or carboxylic acids of the formula CH ₂ =CH(CH ₂ ) _m C0 ₂ R ¹ , wherein R ¹ is hydrogen, hydrocarbyl, or substituted hydrocarbyl, and is 0 or an integer of 1 to 16. It is preferred if R ¹ hydrocarbyl or substituted hydrocarbyl and it is more preferred if it is alkyl containing 1 to 10 carbon atoms, or glycidyl . It is also preferred if m is 0 and/or R is alkyl containing 1 to 10 carbon atoms. It is preferred to make copolymers containing up to about 60 mole percent, preferably up to about 20 mole percent of repeat units derived from the olefinic ester or carboxylic acid.

Total repeat unit units in the polymer herein refer not only to those in the main chain from each monomer unit, but those in branches or side chains as well.

When using (II) , (III) , (IV) or (VII) as a catalyst it is preferred that R ³ and R ⁴ are hydrogen, methyl, or taken together are

(An)

It is also preferred that both R ² and R ⁵ are 2,6- diisopropylphenyl, 2, 6-dimethylphenyl, 4-methylphenyl, phenyl, 2, 6-diethylphenyl, 2,4, 6-trimethylphenyl and 2- t-butylphenyl . When (II) is used, it is preferred that T ¹ is methyl, R ⁶ is methyl or ethyl and R ^' is methyl. When (III) is used it is preferred that T ¹ is methyl and said Lewis base is R ⁶ ₂ 0, wherein R is methyl or ethyl. When (IV) is used it is preferred that R ⁸ is methyl, n is 3 and R ¹ is hydrogen. In addition in Table II are listed all particularly preferred combinations as catalysts for (II) , (III), (IV) and (VII) .

Table II

Com¬ R- ^. TVT ² / M X pound R ⁸

Type

Me OEt ₂ ?d BAF

Me OE ₂ Pd BAF

Me OEt ₂ Ni BAF

Me OEt ₂ Ni BAF

Me OEt ₂ ?d BAF

Me OEt ₂ ?d BAF

Me OEt ₂ Pd SbF _s

Me OEt ₂ Pd BF ₄

Me OEt ₂ Pd PF ₆

Me OEt ₂ Pd SbF _€

Me OEt _: ?d SbF ₆

Me OEt ₂ Pd SbF _€

Me NCMe Pd SbF ₆

Me NCMe Pd SbF _€

Me NCMe Pd BAF

Me NCMe Pd SbF ₆

Me NCMe Pd SbF ₆

^a This group is -CMe ₂ CH ₂ CMe ₂ - ^b This group is -(CH ₂ ) ₃ C0 ₂ Me

When using (II), (III), (IV) or (VII) the temperature at which the polymerization is carried out is about -100°C to about +200°C, preferably about 0°C to about 150°C, more preferably about 25°C to about 100°C. The pressure at which the polymerization is carried out is not critical, atmospheric pressure to about 275 MPa being a suitable range. The pressure can affect the microstructure of the polyolefin produced (see below) .

Catalysts of the formulas (II), (III), (IV) and (VII) may also be supported on a solid catalyst (as opposed to just being added as a solid or in solution) , for instance on silica gel (see Example 98) . By supported is meant that the catalyst may simply be carried physically on the surface of the solid support, may be adsorbed, or carried by the support by other means.

When using (XXX) as a ligand or in any process or reaction herein it is preferred that n is 2, all of R , R and R are hydrogen, and both of R and R are 9-anthracenyl .

Another polymerization process comprises contacting a compound of the formula [Pd(R CN) ₄ ]X ₂ or a combination of Pd[OC(0)R ⁴ ] ₂ and HX, with a compound of the formula

(VIII:

and one or more monomers selected from the group consisting of ethylene, an oiefin of the formula R ¹⁷ CH=CH ₂ or R ¹⁷ CH=CHR ¹⁷ , cyclopentene, cyclobutene, substituted norbornene and norbornene, wherein: R ^" and R are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it; R and R are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R ^" and R ⁴ taken together are hydrocarbylene or substituted hydrocarbylene to form a carbocyclic ring; each R ^" is independently hydrocarbyl or substituted hydrocarbyl provided that R contains no olefinic bonds,- R is hydrocarbyl or substituted hydrocarbyl; and X is a weakly coordinating anion; provided that when norbornene or substituted norbornene is present no other monomer is present . It is believed that in this process a catalyst similar to (II) may be initially generated, and this then causes the polymerization. Therefore, all of the conditions, monomers (including olefinic esters and

carboxylic acids), etc., which are applicable to the process using (II) as a polymerization catalyst are applicable to this process. All preferred items are also the same, including appropriate groups such as R ² , R ³ , R ⁴ , R ⁵ , and combinations thereof. This process however should be run so that all of the ingredients can contact each other, preferably in a single phase. Initially at least, it is preferred that this is done in solution. The molar ratio of (VIII) to palladium compound used is not critical, but for most economical use of the compounds, a moderate excess, about 25 to 100% excess, of (VIII) is preferably used.

As mentioned above, it is believed that in the polymerization using (VIII) and [Pd(R ¹³ CN) ₄ ]X ₂ or a Pd[II] carboxylate a catalyst similar to (II) is formed. Other combinations of starting materials that can combine into catalysts similar to (II) , (III) , (IV) and (VII) often also cause similar polymerizations, see for instance Examples 238 and 239. Also combinations of α-diimines or other diimino ligands described herein with: a nickel [0] or nickel [I] compound, oxygen, an alkyl aluminum compound and an oiefin; a nickel [0] or nickel [I] compound, an acid such as HX and an oiefin; or an α-diimine Ni [0] or nickel [I] complex, oxygen, an alkyl aluminum compound and an oiefin. Thus active catalysts from α-diimines and other bidentate imino compounds can be formed beforehand or in the same "pot" (in situ) in which the polymerization takes place. In all of the polymerizations in which the catalysts are formed in situ, preferred groups on the α-diimines are the same as for the preformed catalysts.

In general Ni[0], Ni[I] or Ni(II) compounds may be used as precursors to active catalyst species. They must have ligands which can be displaced by the appropriate bidentate nitrogen ligand, or must already contain such a bidentate ligand already bound to the nickel atom. Ligands which may be displaced include

1, 5-cyclooctadiene and tris (o-tolyl)phosphite, which may be present in Ni [0] compounds, or dibenzylideneacetone, as in the useful Pd[0] precursor tris (dibenzylideneacetone) dipalladium [0] . These lower valence nickel compounds are believed to be converted into active Ni [II] catalytic species. As such they must also be contacted (react with) with an oxidizing agent and a source of a weakly coordinating anion (X ^" ) . Oxidizing agents include oxygen, KX (wherein X is a weakly coordinating anion) , and other well known oxidizing agents. Sources of X ^" include HX, alkylaluminum compounds, alkali metal and silver salts of X ^" . As can be seen above, some compounds such as HX may act as both an oxidizing agent and a source of X ^" . Compounds containing other lower valent metals may be converted into active catalyst species by similar methods .

When contacted with an alkyl aluminum compound or HX useful Ni [0] compounds include

(XXXIII)

(XXXXII) (XXXXlll)

Various types of Ni [0] compounds are known in the literature. Below are listed references for the types shown immediately above.

• (XXXIII) G. van Koten, et al . , Kέfi .

Organometal. Chem., vol. 21, p. 151-239 (1982) .

• (XXXXII) W. Bonrath, et al. , Angew. Chem. Int. Ed. Engl., vol. 29, p. 298-300 (1990) . • (XXXXIV) H. torn Dieck, et al. , Z.

Natruforsch. , vol. 366, p. 823-832 (1981); and M. Svoboda, et al., J. Organometal. Chem., vol. 191, p. 321-328 (1980) .

• (XXXXV) G. van Koten, et al. , Adv. Organometal. Chem., vol. 21, p. 151-239 (1982) .

In polymerizations using (XIV) , the same preferred monomers and groups (such as R , R , R , R and X) as are preferred for the polymerization using (II) are used and preferred. Likewise, the conditions used and . preferred for polymerizations with (XIV) are similar to those used and preferred for (II) , except that higher oiefin pressures (when the oiefin is a gas) are preferred. Preferred pressures are about 2.0 to about 20 MPa. (XIV) may be prepared by the reaction of one mole of [Pd(R ¹³ CN) ■ ]X ₂ with one mole of (VIII) in acetonitrile or nitromethane.

Novel compound (XIV) is used as an oiefin polymerization catalyst. In preferred forms of (XIV) , the preferred groups R ² , R ³ , R ⁴ , R ⁵ and X are the same as are preferred for compound (II) .

Another type of compound which is an oiefin polymerization catalyst are π-allyl and π-benzyl compounds of the formula

XXXVII wherein M is Ni(II) or Pd(II) ; R ² and R ⁵ are hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound directly to the imino nitrogen

atom has at least two carbon atoms pound to it; R ^" ana

R ,4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R and R taken together are hydrocarbylene or substituted hydrocarbylene to form a ring; X is a weakly coordinating anion; and A is a π- allyl or π-benzyl group. By a π-allyl group is meant a monoanionic with 3 adjacent sp carbon atoms bound to a metal center in an η ³ fashion. The three sp ² carbon atoms may be substituted with other hydrocarbyl groups or functional groups. Typical π-allyl groups include

CC R

wherein R is hydrocarbyl . By a π-benzyl group is meant π-allyl ligand in which two of the sp carbon atoms are part of an aromatic ring, Typical π-benzyl groups include

π-Benzyl compounds usually initiate polymerization of the olefins fairly readily even at room temperature, but π-allyl compounds may not necessarily do so.

Initiation of π-allyl compounds can be improved by using one or more of the following methods:

• Using a higher temperature such as about

80°C.

• Decreasing the bulk of the α-diimine ligand, such as R ² and R ⁵ being 2,6-dimethylphenyl instead of 2,6-diisopropylphenyl.

• Making the π-allyl ligand more bulky, such as using

rather th ^an the simple π-allyl group itself.

• Having a Lewis acid present while using a functional π-allyl or π-benzyl group. 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. When using (XXXVII) as a polymerization catalyst, it is preferred that ethylene and/or a linear α-olefin is the monomer, or cyclopentene, more preferred if the monomer is ethylene and/or propylene, and ethylene is especially preferred. A preferred temperature for the polymerization process using (XXXVII) is about +20°C to about 100°C. It is also preferred that the partial pressure due to ethylene or propylene monomer is at least about 600 kPa.It is also noted that (XXXVII) is a novel compound, and preferred items for (XXXVII) for the polymerization process are also preferred for the compound itself.

Another catalyst for the polymerization of olefins is a compound of the formula

81

(XXXVIII) and one or more monomers selected from the group consisting of ethylene, an oiefin of the formula R ¹⁷ CH=CH ₂ or R ¹⁷ CH=CHR ¹⁷ , cyclobutene, cyclopentene, substituted norbornene, and norbornene, wherein: R and R are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R ³ and R ^"* taken together are hydrocarbylene or substituted hydrocarbylene to form a ring; R is hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound directly to the imino nitrogen atom has at least two carbon atoms bound to it; each R is independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or a functional group; W is alkylene or substituted alkylene containing 2 or more carbon atoms; Z is a neutral Lewis base wherein the donating atom is nitrogen, sulfur, or oxygen, provided that if the donating atom is nitrogen then the pKa of the conjugate acid of that compound (measured in water) is less than about 6, or an oiefin of the formula R ¹⁷ CH=CHR ¹⁷ ; each R ¹ s independently alkyl cr substituted alkyl; and X is a weakly coordinating anion. It is preferred that in compound (XXXVIII) that: R ⁵⁴ is phenyl or substituted phenyl, and preferred substituents are alkyl groups; each R is independently hydrogen or alkyl containing 1 to 10 carbon atoms; W contains 2 carbon atoms between the phenyl ring and metal atom it is bonded to or W is a divalent polymeric group derived from the polymerization of R ¹⁷ CH=CHR ¹⁷ , and it is especially preferred that it is -CH(CH ₃ )CH ₂ - or -C (CH ₃ ) ₂ CH ₂ - ; and Z is a dialkvl ether or an oiefin of the formula

R ¹⁷ CH=CHR ¹⁷ ; and combinations thereof. W is an alkylene group in which each of the two free valencies are to different carbon atoms of the alkylene group. When W is a divalent group formed by the polymerization of R ¹⁷ CH=CHR ¹⁷ , and Z is R ¹⁷ CH=CHR ¹⁷ , the compound (XXXVIII) is believed to be a living ended polymer. That end of W bound to the phenyl ring actually is the original fragment from R from which the "bridge" W originally formed, and the remaining part of W is formed from the oiefin(s) R ¹⁷ CH=CHR ¹⁷ . In a sense this compound is similar in function to compound (VI) .

By substituted phenyl in (XXXVIII) and (XXXIX) is meant the phenyl ring can be substituted with any grouping which does not interfere with the compound's stability or any of the reactions the compound undergoes. Preferred substituents in substituted phenyl are alkyl groups, preferably containing 1 to 10 carbon atoms. Preferred monomers for this polymerization are ethylene and linear α-olefins, or cyclopentene, particularly propylene, and ethylene and propylene or both are more preferred, and ethylene is especially preferred. It is noted that (XXXVIII) is a novel compound, and preferred compounds and groupings are the same as in the polymerization process.

Compound (XXXVIII) can be made by heating compound (XXXIX) ,

wherein: R 3 and R 4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R ³ and R ^* taken together are hydrocarbylene or substituted hydrocarbylene to form a ring; R ⁴ is hydrocarbyl or 5 substituted hydrocarbyl, provided that the carbon atom bound directly to the imino nitrogen atom has at least two carbon atoms bound to it; each R is independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or a functional group; R ⁵ is alkyl containing 2 to 30

10 carbon atoms; T is alkyl; Z is a neutral Lewis base wherein the donating atom is nitrogen, sulfur, or oxygen, provided that if the donating atom is nitrogen then the pKa of the conjugate acid of that compound (measured in water) is less than aoout 6; and X is a

15 weakly coordinating anion. Preferred groups are the same as those in (XXXVIII) . In addition it is preferred that T contain 1 to 10 carbon atoms, and more preferred that it is methyl . A preferred temperature for the conversion of (XXXIX) to (XXXVIII)

20 is about -30°C to about 50°C. Typically the reaction takes about 10 min. to about 5 days, the higher the temperature, the faster the reaction. Another factor which affects the reaction rate is the nature of Z. The weaker the Lewis basicity of Z, the faster the

25 desired reaction will be.

When (II) , (III), (IV) , (V) , (VII), (VIII) or a combination of compounds that will generate similar compounds, (subject to the conditions described above) is used in the polymerization of olefins, cyclolefins,

30 and optionally olefinic esters or carboxylic acids, polymer having what is believed to be similar to a "living end" is formed. This molecule is that from which the polymer grows to its eventual molecular weight . This compound may have the structure

:

wherein: M is Ni(II) or Pd(II) ; R ² and R ⁵ are hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound directly to the imino nitrogen atom has at least two carbon atoms bound to it; R and R ⁴ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R ³ and R ⁴ taken together are hydrocarbylene or substituted hydrocarbylene to form a ring; each R ¹¹ is independently hydrogen, alkyl or - (CH ₂ ) _m C0 ₂ R ¹ ; T ³ is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, R ^1S (C=0)-, R ¹⁵ 0(C=0)-, or -CH ₂ CH ₂ CH ₂ C0 ₂ R ⁸ ; R ¹⁵ is hydrocarbyl not containing olefinic or acetylenic unsaturation; P is a divalent group containing one or more repeat units derived from the polymerization of one or more of ethylene, an oiefin of the formula R ¹⁷ CH=CH ₂ or R ¹⁷ CH=CHR ¹⁷ , cyclobutene, cyclopentene, substituted norbornene, or norbornene and, when M is Pd(II) , optionally one or more compounds of the formula CH ₂ =CH(CH ₂ ) _π ,C0 ₂ R ¹ ; R ⁸ is hydrocarbyl; each R ¹⁷ is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said oiefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms; m is 0 or an integer from 1 to 16; R ¹ is hydrogen, or hydrocarbyl or substituted hydrocarbyl containing 1 to 10 carbon atoms; and X is a weakly coordinating anion; and that when M is Ni(II) , R ¹¹ is not -C0 ₂ R ⁸ and when M is Pd a diene is not present. By an "olefinic ester or carboxylic acid" is meant a compound of the formula

CH ₂ =CH (CH ₂ ) _m C0 ₂ R ¹ , wherein m and R ¹ are as defined immediately above.

This molecule will react with additional monomer (oiefin, cyclic oiefin, olefinic ester or olefinic carboxylic acid) to cause further polymerization. In other words, the additional monomer will be added to P, extending the length of the polymer chain. Thus P may be of any size, from one "repeat unit" to many repeat units, and when the polymerization is over and P is removed from M, as by hydrolysis, P is essentially the polymer product of the polymerization. Polymerizations with (VI) , that is contact of additional monomer with this molecule takes place under the same conditions as described above for the polymeriza ion process using (II) , (III) , (IV) , (V) , (VII) or (VIII) , or combinations of compounds that will generate similar molecules, and where appropriate preferred conditions and structures are the same.

The group T ³ in (VI) was originally the group T ¹ in (II) or (III) , or the group which included R in (IV) . It in essence will normally be one of the end groups of the eventual polymer product. The olefinic group which is coordinated to M, R ^iJ CH=CHR ¹¹ is normally one of the monomers, oiefin, cyclic oiefin, or, if Pd(II) is M, an olefinic ester or carboxylic acid. If more than one of these monomers is present in the reacticn, it may be any one of them. It is preferred that T ³ is alkyl and especially preferred that it is methyl, and it is also preferred that R is hydrogen or n-alkyl. It is also preferred that M is Pd(II) . Another "form" for the living end is (XVI) .

This type of compound is sometimes referred to as a compound in the "agostic state". In fact both (VI) and (XVI) may coexist together in the same polymerization, both types of compound representing living ends. It is believed that (XVI) -type compounds are particularly favored when the end of the growing polymer chain bound to the transition metal is derived from a cyclic oiefin such as cyclopentene. Expressed in terms of the structure of (XVI) this is when both of R ¹¹ are hydrocarbylene to form a carbocyclic ring, and it is preferred that this be a five-membered carbocyclic ring. For both the polymerization process using (XVI) and the structure of (XVI) itself, the same conditions and groups as are used and preferred for (VI) are also used and preferred for (XVI) , with the exception that for R ¹¹ it is preferred in (XVI) that both of R ¹¹ are hydrocarbylene to form a carbocyclic ring.

This invention also concerns a compound of the formula

wherein: M is Ni(II) or Pd(II) ; R ² and R ⁵ are hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound directly to the imino nitrogen atom has at least two carbon atoms bound to it; R ³ and R ⁴ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R ³ and R ⁴ taken together are hydrocarbylene or substituted hydrocarbylene to form a

ring; each R is independently hydrogen, alkyl or [when M is Pd(II)] - (CH ₂ ) _m C0 ₂ R ¹ ; R ¹ is hydrogen, or hydrocarbyl or substituted hydrocarbyl containing 1 to 10 carbon atoms; T ⁴ is alkyl, -R ⁶⁰ C(O)OR ⁸ , R ¹⁵ (C=0)- or R ¹ OC(=0)-; R ¹⁵ is hydrocarbyl not containing olefinic or acetylenic bonds; R is alkylene not containing olefinic or acetylenic bonds; R is hydrocarbyl; and X is a weakly coordinating anion.

(IX) may also be used to polymerize olefins, cyclic olefins, and optionally olefinic esters and carboxylic acids. The same conditions (except as noted below) apply to the polymerizations using (IX) as they do for (VI) . It is preferred that M is Pd(II) and T ⁴ is methyl . A compound of formula (V) may also be used as a catalyst for the polymerization of olefins, cyclic olefins, and optionally olefinic esters and/or carboxylic acids. In this process (V) is contacted with one or more of the essential monomers. Optionally a source of a relatively weakly coordinating anion may also be present. Such a source could be an alkali metal salt of BAF or AgX (wherein X is the anion) , etc. Preferably about 1 mole of the source of X, such as AgX, will be added per mole of (V) . This will usually be done in the liquid phase, preferably in which (V) and the source of the anion are at least partially soluble. The conditions of this polymerization are otherwise the same as described above for (II) , (III) , (IV) and (VII) , including the preferred conditions and ingredients .

In polymerizations using (XX) as the catalyst, a first compound which is a source of a relatively noncoordinating monoanion is present . Such a source can be an alkali metal or silver salt of the monoanion.

(XX)

It is preferred that the alkali metal cation is sodium or potassium. It is preferred that the monoanion is SbF _s ^" , BAF, PF ₆ ^" , or BF ₄ ^" , and more preferred that it is BAF. It is preferred that T ¹ is methyl and/or S is chlorine. All other preferred groups and conditions for these polymerizations are the same as for polymerizations with (II) .

In all of the above polymerizations, and the catalysts for making them it is preferred that R ² and R , if present, are 2,6-diisopropylphenyl and R and R ⁴ are hydrogen or methyl. When cyclopentene is polymerized, is preferred that R ² and R ^s (if present) are 2,6-dimethylphenyl or 2,4,6-trimethylphenyl and that R ³ and R* taken together are An. R ² , R ³ , R ⁴ and R ⁵ and other groups herein may also be substituted hydrocarbyl. As previously defined, the substituent groups in substituted hydrocarbyl groups (there may be one or more substituent groups) should not substantially interfere with the polymerization or other reactions that the compound is undergoing. Whether a particular group will interfere can first be judged from the artisans general knowledge and the particular polymerization or other reaction that is involved. For instance, in polymerizations where an alkyl aluminum compound is used may not be compatible with the presence of groups containing an active (relatively acidic) hydrogen atom, such as hydroxyl or carboxyl because of the known reaction of alkyl aluminum compounds with such active hydrogen containing groups (but such polymerizations may be possible if

89

enough "extra" alkyl aluminum compound is added to react with these groups) . However, in very similar polymerizations where alkyl aluminum compounds are not present, these groups containing active hydrogen may be present. Indeed many of the polymerization processes described herein are remarkably tolerant to the presence of various functional groups. Probably the most important considerations as to the operability of compounds containing any particular functional group are the effect of the group on the coordination of the metal atom (if present) , and side reaction of the group with other process ingredients (such as noted above) . Therefore of course, the further away from the metal atom the functional group is, the less likely it is to influence, say, a polymerization. If there is doubt as to whether a particular functional group, in a particular position, will affect a reaction, simple minimal experimentation will provide the requisite answer. Functional groups which may be present in R , R , R , R , and other similar radicals herein include hydroxy, halo (fluoro, chloro, bromo and iodo) , ether, ester, dialkylamino, carboxy, oxo (keto and aldehyo) , nitro, amide, thioether, and imino. Preferred functional groups are hydroxy, halo, ether and dialkylamino.

Also in all of the polymerizations, the (cyclo)olefin may be substituted hydrocarbyl. Suitable substituents include ether, keto, aldehyde, ester, carboxylic acid. In all of the above polymerizations, with the exceptions noted below, the following monomer (s) , to produce the corresponding homo- or copolymers, are preferred to be used: ethylene; propylene; ethylene and propylene; ethylene and an α-olefin; an α-olefin; ethylene and an alkyl acrylate, especially methyl acrylate; ethylene and acrylic acid; ethylene and carbon monoxide; ethylene, and carbon monoxide and an acrylate ester or acrylic acid, especially methyl

acrylate; propylene and alkyl acrylate, especially methyl acrylate; cyclopentene; cyclopentene and ethylene; cyclopentene and propylene. Monomers which contain a carbonyl group, including esters, carboxylic acids, carbon monoxide, vinyl ketones, etc. , can be polymerized with Pd(II) containing catalysts herein, with the exception of those that require the presence of a neutral or cationic Lewis acid or cationic Bronsted acid, which is usually called the "first compound" in claims describing such polymerization processes.

Another useful "monomer" for these polymerization processes is a C ₄ refinery catalytic cracker stream, which will often contain a mixture of n-butane, isobutane, isobutene, l-butene, 2-butenes and small amounts of butadiene. This type of stream is referred to herein as a "crude butenes stream" . This stream may act as both the monomer source and "solvent" for the polymerization. It is preferred that the concentration of 1- and 2-butenes in the stream be as high as possible, since these are the preferred compounds to be polymerized. The butadiene content should be minimized because it may be a polymerization catalyst poison. The isobutene may have been previously removed for other uses. After being used in the polymerization (during which much or most of the 1- butene would have been polymerized) , the butenes stream can be returned to the refinery for further processing.

In many of the these polymerizations certain general trends may be noted, although for all of these trends there are exceptions. These trends (and exceptions) can be gleaned from the Examples.

Pressure of the monomers (especially gaseous monomers such as ethylene) has an effect on the polymerizations in many instances. Higher pressure often affects the polymer microstructure by reducing branching, especially in ethylene containing polymers. This effect is more pronounced for Ni catalysts than Pd

catalysts. Under certain conditions higher pressures also seem to give higher productivities and higher molecular weight. When an acrylate is present and a Pd catalyst is used, increasing pressure seems to decrease the acrylate content in the resulting copolymer.

Temperature also affects these polymerizations. Higher temperature usually increases branching with Ni catalysts, but often has little such effect using Pd catalysts. With Ni catalysts, higher temperatures appear to often decrease molecular weight. With Pd catalysts, when acrylates are present, increasing temperature usually increases the acrylate content of the polymer, but also often decreases the productivity and molecular weight of the polymer. Anions surprisingly also often affect molecular weight of the polymer formed. More highly coordinating anions often give lower molecular weight polymers. Although all of the anions useful herein are relatively weakly coordinating, some are more strongly coordinating than others. The coordinating ability of such anions is known and has been discussed in the literature, 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. The results found herein in which the molecular weight of the polymer produced is related to the coordinating ability of the anion used, is in line with the coordinating abilities of these anions as described in Beck (p. 1411) and Strauss (p. 932, Table II) .

In addition to the "traditional" weakly coordinating anions cited in the paragraph immediately above, heterogeneous anions may also be employed. In these cases, the true nature of the counterion is poorly defined or unknown. Included in this group are MAO, MMAO and related aluminoxanes which do not form true solutions. The resulting counterions are thought to bear anionic aluminate moieties related to those

cited in the paragraph immediately above. Polymeric anionic materials such as Nafion" polyfluorosulfonic acid can function as non-coordinating counterions. In addition, a wide variety of heterogeneous inorganic materials can be made to function as non-coordinating counterions. Examples would include aluminas, silicas, silica/aluminas, cordierites, clays, MgCl ₂ , and many others utilized as traditional supports for Ziegler- Natta oiefin polymerization catalysts. These are generally materials which have Lewis or Bronsted acidity. High surface area is usually desired and often these materials will have been activated through some heating process. Heating may remove excess surface water and change the surface acidity from Bronsted to Lewis type. Materials which are not active in the role may often be made active by surface treatment. For instance, a surface-hydrated silica, zinc oxide or carbon can be treated with an organoaluminum compound to provide the required functionality.

The catalysts described herein can be heterogenized through a variety of means. The heterogeneous anions in the paragraph immediately above will all serve to heterogenize the catalysts. Catalysts can also be heterogenized by exposing them to small quantities of a monomer to encapsulate them in a polymeric material through which additional monomers will diffuse. Another method is to spray-dry the catalyst with its suitable non-coordinating counterion onto a polymeric support. Heterogeneous versions of the catalyst are particularly useful for running gas- phase polymerizations. The catalyst is suitably diluted and dispersed on the surface of the catalyst support to control the heat of polymerization. When applied to fluidized-bed polymerizations, the heterogeneous supports provide a convenient means of catalyst introduction.

Anions have been found to have another unexpected effect. They can effect the amount of incorporation of an acrylic monomer such as an ester into an olefin/acrylic copolymer. For instance it has been found that SbFg ^" anion incorporates more fluorinated alkyl acrylate ester into an ethylene copolymer than BAF anion, see for instance Example 302.

Another item may effect the incorporation of polar monomers such as acrylic esters in oiefin copolymers. It has been found that catalysts containing less bulky α-diimines incorporate more of the polar monomer into the polymer (one obtains a polymer with a higher percentage of polar monomer) than a catalyst containing a more bulky α-diimine, particularly when ethylene is the oiefin comonomer. For instance, in an α-diimine of formula (VIII) , if R ² and R are 2 , 6-dimethylphenyl instead of 2, 6-diisopropylphenyl, more acrylic monomer will be incorporated into the polymer. However, another common effect of using a less bulky catalyst is to produce a polymer with lower molecular weight.

Therefore one may have to make a compromise between polar monomer content in the polymer and polymer molecular weight.

When an olefinic carboxylic acid is polymerized into the polymer, the polymer will of course contain carboxyl groups . Similarly in an ester containing polymer, some or all of the ester groups may be hydrolyzed to carboxyl groups (and vice versa) . The carboxyl groups may be partially or completely converted into salts such as metallic salts. Such polymeric salts are termed ionomers . Ionomers are useful in adhesives, as ionomeric elastomers, and as molding resins. Salts may be made with ions of metals such as Na, K, Zn, Mg, Al,' etc. The polymeric salts may be made by methods known to the artisan, for instance reaction of the carboxylic acid containing polymers with various compounds of the metals such as bases (hydroxides, carbonates, etc.) or other

compounds, such as acetylacetonates. Novel polymers that contain carboxylic acid groups herein, also form novel ionomers when the carboxylic acid groups are partially or fully converted to carboxylate salts. When copolymers of an olefinic carboxylic acid or olefinic ester and selected olefins are made, they may be crosslinked by various methods known in the art, depending on the specific monomers used to make the polymer. For instance, carboxyl or ester containing polymers may be crosslinked by reaction with diamines to form bisamides. Certain functional groups which may be present on the polymer may be induced to react to crosslink the polymer. For instance epoxy groups (which may be present as glycidyl esters) may be crosslinked by reaction of the epoxy groups, see for instance Example 135.

It has also been found that certain fluorinated olefins, some of them containing other functional groups may be polymerized by nickel and palladium catalysts. Note that these fluorinated olefins are included within the definition of H ₂ C=CHR ¹⁷ , wherein R ¹⁷ can be considered to be substituted hydrocarbyl, the substitution being fluorine and possibly other substituents. Olefins which may be polymerized include H ₂ C=CH(CH ₂ ) _a R _£ R ⁴² wherein a is an integer of 2 to 20, R _f is perfluoroalkylene optionally containing one or more ether groups, and R ⁴² is fluorine or a functional group. Suitable functional groups include hydrogen, chlorine, bromine or iodine, ester, sulfonic acid (- S0 ₃ H) , and sulfonyl halide. Preferred groups for R ⁴² include fluorine, ester, sulfonic acid, and sulfonyl fluoride. A sulfonic acid group containing monomer does not have to be polymerized directly. It is preferably made by hydrolysis of a sulfonyl halide group already present in an already made polymer. It is preferred that the perfluoroalkylene group contain 2 to 20 carbon atoms and preferred perfluoroalkylene groups are -(CF ₂ ) _b - wherein b is 2 to 20, and -

95

(CF ₂ ) _d OCF ₂ CF ₂ - wherein d is 2 to 20. A preferred olefinic comonomer is ethylene or a linear α-olefin, and ethylene is especially preferred. Polymerizations may be carried out with many of the catalysts described herein, see Examples 284 to 293.

As described herein, the resulting fluorinated polymers often don't contain the expected amount of branching, and/or the lengths of the branches present are not those expected for a simple vinyl polymerization.

The resulting polymers may be useful for compatibilizing fluorinated and nonfluorinated polymers, for changing the surface characteristics of fluorinated or nonfluorinated polymers (by being mixed with them) , as molding resins, etc. Those polymers containing functional groups may be useful where those functional groups may react or be catalysts. For instance, if a polymer is made with a sulfonyl fluoride group (R is sulfonyl fluoride) that group may be hydrolyzed to a sulfonic acid, which being highly fluorinated is well known to be a very strong acid. Thus the polymer may be used as an acid catalyst, for example for the polymerization of cyclic ethers such as tetrahydrofuran. In this use it has been found that this polymer is more effective than a completely fluorinated sulfonic acid containing polymer. For such uses the sulfonic acid content need not be high, say only 1 to 20 mole percent, preferably about 2 to 10 mole percent of the repeat units in the polymer having sulfonic acid groups. The polymer may be crosslinked, in which case it may be soluble in the medium (for instance tetrahydrofuran) , or it may be crosslinked so it swollen but not dissolved by the medium, Or it may be coated onto a substrate and optionally chemically attached and/or crosslinked, so it may easily be separated from the other process ingredients.

One of the monomers that may be polymerized by the above catalysts is ethylene (E) , either by itself to form a homopolymer, or with α-olefins and/or olefinic esters or carboxylic acids. The structure of the polymer may be unique in terms of several measurable properties.

These polymers, and others herein, can have unique structures in terms of the branching in the polymer. Branching may be determined by NMR spectroscopy (see the Examples for details) , and this analysis can determine the total number of branches, and to some extent the length of the branches. Herein the amount of branching is expressed as the number of branches per 1000 of the total methylene (-CH ₂ -) groups in the polymer, with one exception. Methylene groups that are in an ester grouping, i.e. -C0 ₂ E, are not counted as part of the 1000 methylenes. These methylene groups include those in the main chain and in the branches. These polymers, which are E homopolymers, have a branch content of about 80 to about 150 branches per 1000 methylene groups, preferably about 100 to about 130 branches per 1000 methylene groups. These branches do not include polymer end groups. In addition the distribution of the sizes (lengths) of the branches is unique. Of the above total branches, for every 100 that are methyl, about 30 to about 90 are ethyl, about 4 to about 20 are propyl, about 15 to about 50 butyl, about 3 to about 15 are amyl, and about 30 to about 140 are hexyl or longer, and it is preferred that for every 100 that are methyl, about 50 to about 75 are ethyl, about 5 to about 15 are propyl, about 24 to about 40 are butyl, about 5 to 10 are amyl, and about 65 to about 120 are hexyl or larger. These E homopolymers are often amorphous, although in some there may be a small amount of crystallinity.

Another polyolefin, which is an E homopolymer that can be made by these catalysts has about 20 to about 150 branches per 1000 methylene groups, and, per 100

methyl groups, about 4 to about 20 ethyl groups, about

1 to about 12 propyl groups, about 1 to about 12 butyl group, about 1 to about 10 amyl groups, and 0 to about

20 hexyl or larger groups. Preferably this polymer has about 40 to about 100 methyl groups per 1000 methylene groups, and per 100 methyl groups, about 6 to about 15 ethyl groups, about 2 to about 10 propyl groups, about 2 to about 10 butyl groups, about 2 to about 3 amyl groups, and about 2 to about 15 hexyl or larger groups. Many of the polyolefins herein, including homopolyethylenes, may be crosslinked by various methods known in the art, for instance by the use of peroxide or other radical generating species which can crosslink these polymers. Such crosslinked polymers are novel when the uncrosslinked polymers from which they are derived are novel, because for the most part the structural feature (s) of the uncrosslinked polymers which make them novel will be carried over into the crosslinked forms. In addition, some of the E homopolymers have an exceptionally low density, less than about 0.86 g/mL, preferably about 0.85 g/mL or less, measured at 25°C. This density is based on solid polymer.

Homopolymers of polypropylene (P) can also have unusual structures. Similar effects have been observed with other α-olefins (e.g. 1-hexene) . A "normal" P homopolymer will have one methyl group for each methylene group (or 1000 methyl groups per 1000 methylene groups) , since the normal repeat unit is - CH(CH ₃ )CH ₂ -. However, using a catalyst of formula (I) in which M is Ni(II) in combination with an alkyl aluminum compound it is possible to produce a P homopolymer with about 400 to about 600 methyl groups per 1000 methylene groups, preferably about 450 to about 550 methyl groups per 1000 methylene groups.

Similar effects have been observed with other α-olefins (e.g. 1-hexene) .

In the polymerization processes described herein olefinic esters and/or carboxylic acids may also be present, and of course become part of the copolymer formed. These esters may be copolymerized with one or more of E and one or more α-olefins. When copolymerized with E alone polymers with unique structures may be formed.

In many such E/olefinic ester and/or carboxylic acid copolymers the overall branching level and the distribution of branches of various sizes are unusual. In addition, where and how the esters or carboxylic acids occur in the polymer is also unusual. A relatively high proportion of the repeat units derived from the olefinic esters are at the ends of branches. In such copolymers, it is preferred that the repeat units derived from the olefinic esters and carboxylic acids are about 0.1 to 40 mole percent of the total repeat units, more preferably about 1 to about 20 mole percent. In a preferred ester, m is 0 and R ¹ is hydrocarbyl or substituted hydrocarbyl. It is preferred that R ¹ is alkyl containing 1 to 20 carbon atoms, more preferred that it contains 1 to 4 carbon atoms, and especially preferred that R ¹ is methyl.

One such preferred dipolym ^' er has about 60 to 100 methyl groups (excluding methyl groups which are esters) per 1000 methylene groups in the polymer, and contains, per 100 methyl branches, about 45 to about 65 ethyl branches, about 1 to about 3 propyl branches, about 3 to about 10 butyl branches, about 1 to about 3 amyl branches, and about 15 to about 25 hexyl or longer branches. In addition, the ester and carboxylic acid containing repeat units are often distributed mostly at the ends of the branches as follows. If the branches, and the carbon atom to which they are attached to the main chain, are of the formula -CH(CH ₂ ) _n C0 ₂ R ¹ , wherein the CH is part of the main chain, then in some of these polymers about 40 to about 50 mole percent of ester groups are found in branches where n is 5 or more,

about 10 to about 20 mole percent when n is 4 , about 20 to 30 mole percent when n is 1, 2 and 3 and about 5 to about 15 mole percent when n is 0. When n is 0, an acrylate ester has polymerized "normally" as part of the main chain, with the repeat unit -CH^CHCO^ ¹ - .

These branched polymers which contain oiefin and olefinic ester monomer units, particularly copolymers of ethylene and methyl acrylate and/or other acrylic esters are particularly useful as viscosity modifiers for lubricating oils, particularly automotive lubricating oils.

Under certain polymerization conditions, some of the polymerization catalysts described herein produce polymers whose structure is unusual, especially considering from what compounds (monomers) the polymers were made, and the fact that polymerization catalysts used herein are so-called transition metal coordination catalysts (more than one compound may be involved in the catalyst system, one of which must include a transition metal) . Some of these polymers were described in a somewhat different way above, and they may be described as "polyolefins" even though they may contain other monomer units which are not olefins (e.g., olefinic esters) . In the polymerization of an unsaturated compound of the formula H ₂ C=CH (CH ₂ ) _e G, wherein e is 0 or an integer of 1 or more, and G is hydrogen or -COzR ¹ , the usual ("normal") polymeric repeat unit obtained would be -CH ₂ -CH [ (CH ₂ ) _e G] - , wherein the branch has the formula -(CH ₂ ) _e G. However, with some of the instant catalysts a polymeric unit may be -CH ₂ - CH [ (CH ₂ ) _f G] - , wherein f ≠ e, and f is 0 or an integer of 1 or more. If f<e, the "extra" methylene groups may be part of the main polymer chain. If f>e (parts of) additional monomer molecules may be incorporated into that branch. In other words, the structure of any polymeric unit may be irregular and different for monomer molecules incorporated into the polymer, and the structure of such a polymeric unit obtained could

be rationalized as the result of "migration o ^' f the active polymerizing site" up and down the polymer chain, although this may not be the actual mechanism. This is highly unusual, particularly for 5 polymerizations employing transition metal coordination catalysts.

For "normal" polymerizations, wherein the polymeric unit -CH ₂ -CH[ (CH ₂ ) _e G] - is obtained, the theoretical amount of branching, as measured by the 10 number of branches per 1000 methylene (-CH ₂ -) groups can be calculated as follows which defines terms "theoretical branches" or "theoretical branching" herein:

I D Theoretical branches - mnrnTotal mole fract ion of α-olef ms

{ [I (2*mole fraction e»0) ] + [Kmole fraction u-olefin*e) ] }

In this equation, an α-olefin is any olefinic compound H ₂ C=CH(CH ₂ ) _e G wherein e≠O. Ethylene or an acrylic 0 compound are the cases wherein e=0. Thus to calculate the number of theoretical branches in a polymer made from 50 mole percent ethylene (e=0) , 30 mole percent propylene (e=l) and 20 mole percent methyl 5-heptenoate (e=4) would be as follows: 5

Theoretical oranches • lootmo . s - 238 (branches/1000 •ner.hyleneε i

{ [ (2*0.5) I * ( (0.30*1) * 10.20*4 I ) |

The "1000 methylenes" include all of the methylene 0 groups in the polymer, including methylene groups in the branches.

For some of the polymerizations described herein, the actual amount of branching present in the polymer is considerably greater than or less than the above 5 theoretical branching calculations would indicate. For instance, when an ethylene homopolymer is made, there should be no branches, yet there are often many such branches. When an α-olefin is polymerized, the

branching level may be much lower or higher than the theoretical branching level. It is preferred that the actual branching level is at 90% or less of the theoretical branching level, more preferably about 80% or less of the theoretical branching level, or 110% or more of the theoretical branching level, more preferably about 120% or more of the theoretical branching level. The polymer should also have at least about 50 branches per 1000 methylene units, preferably about 75 branches per 1000 methylene units, and more preferably about 100 branches per 1000 methylene units. In cases where there are "0" branches theoretically present, as in ethylene homopolymers or copolymers with acrylics, excess branches as a percentage cannot be calculated. In that instance if the polymer has 50 or more, preferably 75 or more branches per 1000 methylene groups, it has excess branches (i.e. in branches in which f>0) .

These polymers also have "at least two branches of different lengths containing less than 6 carbon atoms each." By this is meant that branches of at least two different lengths (i.e. number of carbon atoms) , and containing less than 6 carbon atoms, are present m the polymer. For instance the polymer may contain ethyl and butyl branches, or methyl and amyl branches.

As will be understood from the above discussion, the lengths of the branches ("f") do not necessarily correspond to the original sizes of the monomers used ("e") . Indeed branch lengths are often present which do not correspond to the sizes of any of the monomers used and/or a branch length may be present "in excess" . By "in excess" is meant there are more branches of a particular length present than there were monomers which corresponded to that branch length in the polymer. For instance, in the copolymerization of 75 mole percent ethylene and 25 mole percent l-butene it would be expected that there would be 125 ethyl branches per 1000 methylene carbon atoms. If there

were more ethyl branches than that, be- ITΪ excess compared to the theoretical branching. There may also be a deficit of specific length branches. If there were less than 125 ethyl branches per 1000 methylene groups in this polymer there would be a deficit. Preferred polymers have 90% or less or 110% or more of the theoretical amount of any branch length present in the polymer, and it is especially preferred if these branches are about 80% or less or- about 120% or more of the theoretical amount of any branch length. In the case of the 75 mole percent ethylene/25 mole percent l-butene polymer, the 90% would be about 113 ethyl branches or less, while the 110% would be about 138 ethyl branches or more. Such polymers may also or exclusively contain at least 50 branches per 1000 methylene atoms with lengths which should not theoretically (as described above) be present at all.

These polymers also have "at least two branches of different lengths containing less than 6 carbon atoms each." By this is meant that branches of at least two different lengths (i.e. number of carbon atoms), and containing less than 6 carbon atoms, are present in the polymer. For instance the polymer may contain ethyl and butyl branches, or methyl and amyl branches. Some of the polymers produced herein are novel because of unusual structural features. Normally, in polymers of alpha-olefins of the formula CH =CH(CH ₂ ) _a H wherein a is an integer of 2 or more made by coordination polymerization, the most abundant, and often the only, branches present in such polymers have the structure -(CH ₂ ) _a H. Some of the polymers produced herein are novel because methyl branches comprise about 25% to about 75% of the total branches in the polymer. Such polymers are described in Examples 139, 162, 173 and 243-245. Some of the polymers produced herein are novel because in addition to having a high percentage (25-75%) of methyl branches (of the total branches present) , they also contain linear branches of the

structure -{CH ₂ ) _n H wherein n is an integer of six or greater. Such polymers are described in Examples 139, 173 and 243-245. Some of the polymers produced herein are novel because in addition to having a high percentage (25-75%) of methyl branches (of the total branches present) , they also contain the structure (XXVI) , preferably in amounts greater than can be accounted for by end groups, and more preferably greater than 0.5 (XXVI) groups per thousand methyl groups in the polymer greater than can be accounted for by end groups .

CH ₃ I —CH ₂ -CH-(CH ₂ ) _a H (XXVI)

Normally, homo- and copolymers of one or more alpha-olefins of the formula CH =CH ^CH ₂ ) _a H wherein a is an integer of 2 or more contain as part of the polymer backbone the structure (XXV)

p35 R 6

I I —CH-CH ₂ -CH— (XXV)

wherein R ³⁵ and R ³⁶ are alkyl groups. In most such polymers of alpha-olefins of this formula (especially those produced by coordination-type polymerizations) , both of R ³⁵ and R ³⁶ are -(CH ) _a H. However, in certain of these polymers described herein, about 2 mole percent or more, preferably about 5 mole percent or more and more preferably about 50 mole percent or more of the total amount of (XXV) in said polymer consists of the structure where one of R ³⁵ and R ³⁶ is a methyl group and the other is an alkyl group containing two or more carbon atoms. Furthermore, m certain of these polymers described herein, structure (XXV) may occur in side chains as well as in the polymer backbone. Structure (XXV) can be detected by ¹³ C NMR. The signal

for the carbon atom of the methylene group between the two methine carbons in (XXV) usually occurs in the ¹³ C NMR at 41.9 to 44.0 ppm when one of R ³⁵ and R ³⁶ is a methyl group and the other is an alkyl group containing two or more carbon atoms, while when both R ³⁵ and R ³⁶ contain 2 or more carbon atoms, the signal for the methylene carbon atom occurs at 39.5 to 41.9 ppm. Integration provides the relative amounts of these structures present in the polymer. If there are interfering signals from other carbon atoms in these regions, they must be subtracted from the total integrals to give correct values for structure (XXV) .

Normally, homo- and copolymers of one or more alpha-olefins of the formula CH ₂ =CH(CH ₂ ) _a H wherein a is an integer of 2 or more (especially those made by coordination polymerization) contain as part of the polymer backbone structure (XXIV) wherein n is 0, 1, or 2. When n is 0, this structure is termed "head to head" polymerization. When n is 1, this structure is termed "head to tail" polymerization. When n is 2, this structure is termed "tail to tail" polymerization. In most such polymers of alpha-olefins of this formula (especially those produced by coordination-type polymerizations), both of R ³⁷ and R ^3B are -(CH ₂ )a ^H - However some of the polymers of alpha-olefins of this formula described herein are novel in that they also contain structure (XXIV) wherein n = a, R ³⁷ is a methyl group, and R ³⁸ is an alkyl group with 2 or more carbon atoms.

R37 R38

I I

—CH—(CH ₂ ) _n —CH—

(XXIV)

Normally polyethylene made by coordination polymerization has a linear backbone with either no

branching, or small amounts of linear branches. Some of the polyethylenes described herein are unusual in that they contain structure (XXVII) which has a methine carbon that is not part of the main polymer backbone.

CH ₃ I —CH ₂ -CH-CH ₂ CH ₃ (XXVII)

Normally, polypropylene made by coordination polymerization has methyl branches and few if any branches of other sizes. Some of the polypropylenes described herein are unusual in that they contain one or both of the structures (XXVIII) and (XXIX) .

CH ₃

— ( XVMI) CH ₃

I —CH ₂ CH ₂ -CH-CH ₃ (XXIX)

As the artisan understands, in coordination polymerization alpha-olefins of the formula CH ₂ =CH (CH ) _a H may insert into the growing polymer chain in a 1, 2 or 2, 1 manner. Normally these insertion steps lead to 1,2- enchainment or 2, 1-enchainment of the monomer. Both of these fundamental steps form a - (CH ₂ ) _a H branch. However, with some catalysts herein, some of the initial product of 1,2 insertion can rearrange by migration of the coordinated metal atom to the end of the last inserted monomer before insertion of additional monomer occurs. This results in omega, 2- enchainment and the formation of a methyl branch.

1 ,2 insertion polymer-M + CH ₂ =CH(CH ₂ ),H

polymer''

1 ,2-enchaιnment (o,2-enchainment -(CH ₂ ).H branch -CH ₃ branch

It is also known that with certain other catalysts, some of the initial product of 2,1 insertion can rearrange in a similar manner by migration of the coordinated metal atom to the end of the last inserted monomer. This results in omega,1-enchainment and no branch is formed.

2,1 insertion polymer-M + CH ₂ *CH(CH ₂ ) _a H

M l polymer- -CH. rearrangement . _ _u

CHj .,«n . _u ^a » ^» - polymer — _^ .CH^

( ^CH 2). ^H CH ₂ ² ^(CH ₂ ),M

2.1 -enchainment (0,1-enchaιnment -(CH ₂ ) _a H branch no branch

Of the four types of alpha-olefin enchainment, omega,1-enchainment is unique in that it does not generate a branch. In a polymer made from an alpha- olefin of the formula CH ₂ =CH(CH2) _a ^H » ^trιe total number of branches per 1000 methylene groups (B) can be expressed as:

B = (1000) (1-X _ω(1 )/[(1-X _ω ,ι)a + X _ω ,ι(a + 2)] where X _ω, ι is the fraction of omega,1-enchainment

Solving this expression for X _ω ,ι gives:

X _ω ,ι = (1000 - aB)/(1000 + 2B)

This equation provides a means of calculating the fraction of omega,1-enchainment in a polymer of a linear alpha-olefin from the total branching B. Total branching can be measured by ¹ H NMR or ¹³ C NMR. Similar equations can be written for branched alpha-

olefins. For example, the equa ion for 4-methyl-1- pentene is:

X _ω, ι = (2000 - 2B)/(1000 + 2B) Most polymers of alpha-olefins made by other coordination polymerization methods have less than 5% omega, 1-enchainment. Some of the alpha-olefin polymers described herein have unusually large amounts (say >5%) of omega, 1-enchainment . In essence this is similar to stating that a polymer made from an α-olefin has much less than the "expected" amount of branching. Although many of the polymerizations described herein give substantial amounts of ω,l- and other unusual forms of enchainment of olefinic monomers, it has surprisingly been found that "unsymmetrical" α-diimine ligands of formula (VIII) give especially high amounts of ω,l- enchain ent . In particular when R ^" and R are phenyl, and one or both of these is substituted in such a way as different sized groups are present in the 2 and 6 position of the phenyl ring(s) , ω, 1-enchainment is enhanced. For instance, if one or both of R and R ⁵ are 2- -butylphenyl, this enchainment is enhanced. In this context when R and/or R are "substituted" phenyl the substitution may be not only in the 2 and/or 6 positions, but on any other position in the phenyl ring. For instance, 2, 5-di-t-butylphenyl, and 2-t- butyl-4 , 6-dichlorophenyl would be included in substituted phenyl.

The steric effect of various groupings has been quantified by a parameter called E _s , see R. W. Taft, Jr., J. Am. Chem. Soc . , vol. 74, p. 3120-3128, and M.S. Newman, Steric Effects in Organic Chemistry, John Wiley & Sons, New York, 1956, p. 598-603. For the purposes herein, the E _s values are those fcr o-substituted benzoates described in these publications. If the value fcr E _s for any particular group is not known, it can be determined by methods described in these publications. For the purposes herein, the value of hydrogen is defined to be the same as for methyl. It

is preferred that difference in E _a , when R""Tanτι preferably also R ⁵ ) is phenyl, between the groups substituted in the 2 and 6 positions of the phenyl ring is at least 0.15, more preferably at least about 0.20, and especially preferably about 0.6 or more. These phenyl groups may be unsubstituted or substituted in any other manner in the 3, 4 or 5 positions.

These differences in E _a are preferred in a diimine such as (VIII) , and in any of the polymerization processes herein"wherein a metal complex containing an α-diimine ligand is used or formed. The synthesis and use of such α-diimines is illustrated in Examples 454- 463.

Because of the relatively large amounts of ω,l- enchainment that may be obtained using some of the polymerization catalysts reported herein novel polymers can be made. Among these homopolypropylene (PP) . In some of the PP's made herein the structure

C HCH ₂ CH C H (C H ₂ ) _n C H CH CH C H

(XXXX) may be found. In this structure each C ^a is a methine carbon atom that is a branch point, while each C is a methylene group that is more than 3 carbon atoms removed from any branch point (C ^a ) . Herein methylene groups of the type -C^- are termed δ+ (or delta+) methylene groups. Methylene groups of the type -C ^d H ₂ - - which are exactly the third carbon atom from a branch point, are termed γ (gamma) methylene groups. The NMR signal for the δ+ methylene groups occurs at about 29.75 ppm, while the NMR signal for the γ methylene groups appears at about 30.15 ppm. Ratios of these types of methylene groups to each other and the total number of methylene groups in the PP is done by the usual NMR integration techniques.

It is preferred that PP's made herein have about 25 to about 300 δ+ methylene groups per 1000 methylene groups (total) in the PP.

It is also preferred that the ratio of δ+:γ methylene groups in the PP be 0.7 to about 2.0.

The above ratios involving δ+ and γ methylene groups in PP are of course due to the fact that high relatively high ω,l enchainment can be obtained. It is preferred that about 30 to 60 mole percent of the monomer units in PP be enchained in an ω, 1 fashion. Using the above equation, the percent ω,l enchainment for polypropylene can be calculated as:

% ω,l = (100) (1000-B) / (1000+2B) wherein B is the total branching (number of methyl groups) per 1000 methylene groups in the polymer. Homo- or copolymers of one or more linear α- olefins containing 3 to 8 carbon atoms may also have δ+ carbon atoms in them, preferably at least about 1 or more δ+ carbon atoms per 1000 methylene groups. The above polymerization processes can of course be used to make relatively random copolymers (except for certain CO copolymers) of various possible monomers. However, some of them can also be used to make block polymers. A block polymer is conventionally defined as a polymer comprising molecules in which there is a linear arrangement of blocks, a block being a portion of a polymer molecule which the monomeric units have at least one constitutional or configurational feature absent from adjacent portions (definition from H. Mark, et al . , Ed., Encyclopedia of Polymer Science and Engineering, Vol. 2, John Wiley & Sons, New York, 1985, p. 324) . Herein in a block copolymer, the constitutional difference is a difference in monomer units used to make that block, while in a block homopolymer the same monomer (s) are used but the repeat units making up different blocks are different structure and/or ratios of types of structures .

10

Since it is believed that many of the polymerization processes herein have characteristics that often resemble those of living polymerizations, making block polymers may be relatively easy. One method is to simply allow monomer(s) that are being polymerized to be depleted to a low level, and then adding different monomer(s) or the same combination of monomers in different ratios. This process may be repeated to obtain polymers with many blocks. Lower temperatures, say about less than 0°C, preferably about -10° to about -30°, tends to enhance the livingness of the polymerizations. Under these conditions narrow molecular weight distribution polymers may be obtained (see Examples 367-369 and 371) , and block copolymers may also be made (Example 370) .

As pointed out above, certain polymerization conditions, such as pressure, affect the microstructure of many polymers. The microstructure in turn affects many polymer properties, such as crystallization.

Thus, by changing polymerization conditions, such as the pressure, one can change the microstructure of the part of the polymer made under those conditions. This of course leads to a block polymer, a polymer have defined portions having structures different from other defined portions. This may be done with more than one monomer to obtain a block copolymer, or may be done with a single monomer or single mixture of monomers to obtain a block homopolymer. For instance, in the polymerization of ethylene, high pressure sometimes leads to crystalline polymers, while lower pressures give amorphous polymers. Changing the pressure repeatedly could lead to an ethylene homopolymer containing blocks of amorphous polyethylene and blocks of crystalline polyethylene. If the blocks were of the correct size, and there were enough of them, a thermoplastic elastomeric homopolyethylene could be

produced. Similar polymers could possibly be made from other monomer(s), such as propylene.

Homopolymers of α-olefins such as propylene, that is polymers which were made from a monomer that consisted essentially of a single monomer such as propylene, which are made herein, sometimes exhibit unusual properties compared to their "normal" homopolymers. For instance, such a homopolypropylene. usually would have about 1000 methyl groups per 1000 methylene groups. Polypropylenes made herein typically have about half that many methyl groups, and in addition have some longer chain branches. Other α- olefins often give polymers whose microstructure is analogous to these polypropylenes when the above catalysts are used for the polymerization.

These polypropylenes often exhibit exceptionally low glass transition temperatures (Tg's) . "Normal" polypropylene has a Tg of about -17°C, but the polypropylenes herein have a Tg of -30°C or less, preferably about -35°C or less, and more preferably about -40°C or less. These Tg's are measured by Differential Scanning Calorimetry at a heating rate of 10°C/min, and the Tg is taken as the midpoint of the transition. These polypropylenes preferably have at least 50 branches (methyl groups) per 1000 carbon atoms, more preferably at least about 100 branches per 1000 methylene groups.

Previously, when cyclopentene was coordination polymerized to higher molecular weights, the resulting polymer was essentially intractable because of its very high melting point, greatly above 300°C. Using the catalysts here to homopolymerize cyclopentene results in a polymer that is tractable, i.e., may be reformed, as by melt forming. Such polymers have an end of melting point of about 320°C or less, preferably about 300 ^C C or less, or a melting point of about 275 C or less, preferably about 250°C or less. The melting point is determined by Differential Scanning

Calorimetry at a heating rate of 15°C/min, and taking the maximum of the melting endotherm as the melting point. However these polymers tend to have relatively diffuse melting points, so it is preferred to measure the "melting point" by the end of melting point. The method is the same, except the end of melting is taken as the end (high temperature end) of the melting endotherm which is taken as the point at which the DSC signal returns to the original (extrapolated) baseline. Such polymers have an average degree of polymerization (average number of cyclopentene repeat units per polymer chain) of about 10 or more, preferably about 30 or more, and more preferably about 50 or more.

In these polymers, enchainment of the cyclopentene repeat units is usually as cis-1,3-pentylene units, in contrast to many prior art cyclopentenes which were enchained as 1,2-cyclopentylene units. It is preferred that about 90 mole percent or more, more preferably about 95 mole percent or more of the enchained cyclopentene units be enchained as 1,3-cyclopentylene units, which are preferably cis-1,3-cyclopentylene units.

The X-ray powder diffraction pattern of the instant poly(cyclopentenes) is ^" also unique. To produce cyclopentene polymer samples of uniform thickness for X-ray measurements, powder samples were compressed into disks approximately 1 mm thick and 32 mm in diameter. X-ray powder diffraction patterns of the samples were collected over the range 10-50° 2θ. The diffraction data were collected using an automated Philips θ-θ diffracto eter (Philips X'pert System) operating in the symmetrical transmission mode (Ni-filtered CuKa radiation, equipped with a diffracted beam collimator (Philips Thin Film Collimator system) , Xe filled proportional detector, fixed step mode (0.05°/step) , 12.5 sec./step, 1/4° divergence slit). Reflection positions were identified using the peak finding routine in the APD suite of programs provided with the

X'pert System. The X-ray powder diffraction pattern had reflections at approximately 17.3°, 19.3°, 24.2°, and 40.7° 2θ, which correspond to d-spacings of approximately 0.512, 0.460, 0.368 and 0.222 nm, respectively. These polymers have a monoclinic unit cell of the approximate dimensions: a=0.561 nm; b=0.607 nm; c=7.37 nm; and g=123.2°.

Copolymers of cyclopentene and various other olefins may also be made. For instance a copolymer of ethylene and cyclopentene may also be made. In such a copolymer it is preferred that at least 50 mole percent, more preferably at least about 70 mole percent, of the repeat units are derived from cyclopentene. As also noted above, many of the polymerization systems described herein produce polyethylenes that have considerable branching in them. Likewise the ethylene units which are copolymerized with the cyclopentene herein may also be branched, so it is preferred that there be at least 20 branches per 1000 methylene carbon atoms in such copolymers. In this instance, the "methylene carbon atoms" referred to in the previous sentence do not include methylene groups in the cyclopentene rings. Rather it includes methylene groups only derived from ethylene or other oiefin, but not cyclopentene.

Another copolymer that may be prepared is one from cyclopentene and an α-olefin, more preferably a linear α-olefin. It is preferred in such copolymers that repeat units derived from cyclopentene are 50 mole percent or more of the repeat units. As mentioned above, α-olefins may be enchained in a 1,ω fashion, and it is preferred that at least 10 mole percent of the repeat units derived from the α-olefin be enchained in such a fashion. Ethylene may also be copolymerized with the cyclopentene and α-olefin.

Poly(cyclopentene) and copolymers of cyclopentene, especially those that are (semi) crystalline, may be used as molding and extrusion resins. They may contain

various materials normally found in resins, such as fillers, reinforcing agents, antioxidants, antiozonants, pigments, tougheners, compatibilizers, dyes, flame retardant, and the like. These polymers may also be drawn or melt spun into fibers. Suitable tougheners and compatibilizers include polycyclopentene resin which has been grafted with maleic anhydride, an grafted EPDM rubber, a grafted EP rubber, a functionalized styrene/butadiene rubber, or other rubber which has' been modified to selectively bond to components of the two phases.

In all of the above homo- and copolymers of cyclopentene, where appropriate, any of the preferred state may be combined any other preferred state(s) . The homo- and copolymers of cyclopentene described above may used or made into certain forms as described below:

1. The cyclopentene polymers described above may be part of a polymer blend. That is they may be mixed in any proportion with one or more other polymers which may be thermoplastics and/or elastomers. Suitable polymers for blends are listed below in the listing for blends of other polymers described herein. One preferred type of polymer which may be blended is a toughening agent or compatibilizer, which is often elastomeric and/or contains functional groups which may help compatibilize the mixture, such as epoxy or carboxyl.

2. The polycyclopentenes described herein are useful in a nonwoven fabric comprising fibrillated three-dimensional network fibers prepared by using of a polycyclopentene resin as the principal component. It can be made by flash-spinning a homogeneous solution containing a polycyclopentene. The resultant nonwoven fabric is excellent in heat resistance, dimensional stability and solvent resistance.

3. A shaped part of any of the cyclopentene containing resins. This part may be formed by

injection molding, extrusion, and thermoformmg. Exemplary uses include molded part for automotive use, medical treatment container, microwave-range container, food package container such as hot packing container, oven container, retort container, etc., and heat- resisting transparent container such as heat-resisting bottle.

4. A sheet or film of any of the cyclopentene containing resins. This sheet or film may be clear and may be used for optical purposes (i.e. breakage resistant glazing) . The sheet or film may be oriented or unoriented. Orientation may be carried out by any of the known methods such a uniaxial or biaxial drawing. The sheet or film may be stampable or thermoformable.

5. The polycyclopentene resins are useful in nonwoven fabrics or microfibers which are produced by melt-blowing a material containing as a main component a polycyclopentene. A melt-blowing process for producing a fabric or fiber comprises supplying a polycyclopentene in a molten form from at least one orifice of a nozzle into a gas stream which attenuates the molten polymer into microfibers. The nonwoven fabrics are excellent in heat-resistant and chemical resistant characteristics, and are suitable fcr use as medical fabrics, industrial filters, battery separators and so forth. The microfibers are particularly useful in the field of high temperature filtration, coalescing and insulation. 6. A laminate in which one or more of the layers comprises a cyclopentene resin. The laminate may also contain adhesives, and other polymers in some or all of the layers, or other materials such as paper, metal foil, etc. Some or all of the layers, may be oriented in the same or different directions. The laminate as a whole may also be oriented. Such materials are useful for containers, or other uses where barrier properties are required.

7. A fiber of a cyclopentene polymer. This fiber may be undrawn or drawn to further orient it . It is useful for apparel and in industrial application where heat resistance and/or chemical resistance are important.

8. A foam or foamed object of a cyclopentene polymer. The foam may be formed in any conventional manner such as by using blowing agents.

9. The cyclopentene resins may be microporous membranes. They may be used in process wherein semi- permeable membranes are normally used.

In addition, the cyclopentene resins may be treated or mixed with other materials to improve certain properties, as follows: 1. They may further be irradiated with electron rays. This often improves heat resistance and/or chemical resistance, and is relatively inexpensive. Thus the molding is useful as a material required to have high heat resistance, such as a structural material, a food container material, a food wrapping material or an electric or electronic part material, particularly as an electric or electronic part material, because it is excellent in soldering resistance. 2. Parts with a crystallinity of at least 20% may be obtained by subjecting cyclopentene polymers having an end of melting point between 240 and 300°C to heat treatment (annealing) at a temperature of 120°C to just below the melting point of the polymer. Preferred conditions are a temperature of 150 to 280°C. for a period of time of 20 seconds to 90 minutes, preferably to give a cyclopentene polymer which has a heat deformation temperature of from 200 to 260°C. These parts have good physical properties such as heat resistance and chemical resistance, and thus are useful for, for example, general construction materials, electric or electronic devices, and car parts.

3. Cyclopentene resins may be nucleated to promote crystallization during processing. An example would be a polycyclopentene resin composition containing as main components (A) 100 parts by weight of a polycyclopentene and (B) 0.01 to 25 parts by weight of one or more nucleating agents selected from the group consisting of (1) metal salts of organic acids, (2) inorganic compounds, (3) organophosphorus compounds, and/or (4) metal salts of ionic hydrocarbon copolymer. Suitable nucleating agents may be sodium methylenebis (2, 4-di-tertbutylphenyl) acid phosphate, sodium bis (4-tert-butylphenyl) phosphate, aluminum p- (tert-butyl) benzoate, talc, mica, or related species. These could be used in a process for producing polycyclopentene resin moldings by molding the above polycyclopentene resin composition at a temperature above their melting point .

4. Flame retardants and flame retardant combinations may be added to a cyclopentene polymer. Suitable flame retardants include a halogen-based or phosphorus-based flame retardant, antimony trioxide, antimony pentoxide, sodium antimonate, metallic antimony, antimony trichloride, antimony pentachloride, antimony trisulfide, antimony pentasulfide, zinc borate, barium metaborate or zirconium oxide. They may be used in conventional amounts.

5. Antioxidants may be used in conventional amounts to improve the stability of the cyclopentene polymers. For instance 0.005 to 30 parts by weight, per 100 parts by weight of the cyclopentene polymer, of an antioxidant selected from the group consisting of a phosphorous containing antioxidant, a phenolic antioxidant or a combination thereof. The phosphorous containing antioxidant may be a monophosphite or diphosphite or mixture thereof and the phenolic antioxidant may be a dialkyl phenol, trialkyl phenol, diphenylmonoalkoxylphenol, a tetraalkyl phenol, or a mixture thereof. A sulfur-containing antioxidant may

also be used alone or in combination with otrπer antioxidants.

6. Various fillers or reinforcers, such as particulate or fibrous materials, may be added to improve various physical properties.

7. "Special" physical properties can be obtained by the use of specific types of materials. Electrically conductive materials such as fine metallic wires or graphite may be used to render the polymer electrically conductive. The temperature coefficient of expansion may be regulated by the use of appropriate fillers, and it may be possible to even obtain materials with positive coefficients of expansion. Such materials are particularly useful in electrical and electronic parts.

8. The polymer may be crosslinked by irradiation or chemically as by using peroxides, optionally in the presence of suitable coagents. Suitable peroxides include benzpyl peroxide, lauroyl peroxide, dicumyl peroxide, tert-butyl peroxide, tert- butylperoxybenzoate, tert-butylcumyl peroxide, tert- butylhydroperoxide, 2,5-dimethyl-2,5-di(tert- butylperoxy)hexane, 2,5-dimethyl-2,5-di (tert- butylperoxy)hexyne-3,1,1-bis (tert- butylperoxyisopropyl)benzene, 1,1-bis(tert- butylperoxy) -3,3,5- trimethylcyclohexane, n-butyl-4,4- bis (tert-butylperoxy)valerate, 2,2-bis(tert- butylperoxy)butane and tert-butylperoxybenzene.

When polymerizing cyclopentene, it has been found that some of the impurities that may be found in cyclopentene poison or otherwise interfere with the polymerizations described herein. Compounds such as 1,3-pentadiene (which can be removed by passage through 5A molecular sieves) , cyclόpentadiene (which can be removed by distillation from Na) , and methylenecyclobutane (which can be removed by distillation from polyphosphoric acid) , may interfere

with the polymerization, and their level should be kept as low as practically possible.

The above polymers (in general) are useful in many applications. Crystalline high molecular weight polymers are useful as molding resins, and for films for use in packaging. Amorphous resins are useful as elastomers, and may be crosslinked by known methods, such as by using free radicals. When such amorphous resins contain repeat units derived from polar monomers they are oil resistant. Lower molecular weight polymers are useful as oils, such as in polymer processing aids. When they contain polar groups, particularly carboxyl groups, they are useful in adhesives . In many of the above polymerizations, the transition metal compounds employed as (part of the) catalysts contain(s) (a) metal atom(s) in a positive oxidation state. In addition, these complexes may have a square planar configuration about the metal, and the metal, particularly nickel or palladium, may have a d ⁸ electronic configuration. Thus some of these catalysts may be said to have a metal atom which is cationic and has a d ⁸ -square planar configuration.

In addition these catalysts may have a bidentate ligand wherein coordination to the transition metal is through two different nitrogen atoms or through a nitrogen atom and a phosphorus atom, these nitrogen and phosphorus atoms being part of the bidentate ligand. It is believed that some of these compounds herein are effective polymerization catalysts at least partly because the bidentate ligands have sufficient steric bulk on both sides of the coordination plane (of the square planar complex) . Some of the Examples herein with the various catalysts of this type illustrate the degree of steric bulk which may be needed for such catalysts. If such a complex contains a bidentate ligand which has the appropriate steric bulk, it is

believed that it produces polyethylene with a degree σf polymerization of at least about 10 or more.

It is also believed that the polymerization catalysts herein are effective because unpolymerized olefinic monomer can only slowly displace from the complex a coordinated oiefin which may be formed by β- hydride elimination from the growing polymer chain which is attached to the transition metal. The displacement can occur by associative exchange. Increasing the steric bulk of the ligand slows the rate of associative exchange and allows polymer chain growth. A quantitative measure of the steric bulk of the bidentate ligand can be obtained by measuring at - 85°C the rate of exchange of free ethylene with complexed ethylene in a complex of formula (XI) as shown in equation 1 using standard ¹ H NMR techniques, which is called herein the Ethylene Exchange Rate (EER) . The neutral bidentate ligand is represented by YN where Y is either N or P. The EER is measured in this system. In this measurement system the metal is always Pd, the results being applicable to other metals as noted below. Herein it is preferred for catalysts to contain bidentate ligands for which the second order rate constant for Ethylene Exchange Rate is about 20,000 L-mol" ¹ s" ¹ or less when the metal used in the polymerization catalyst is palladium, more preferably about 10,000 L-mol ^_1 s" ¹ or less, and more preferably about 5,000 L-mol ^"1 s ^"1 or less. When the metal in the polymerization catalyst is nickel, the second order rate constant (for the ligand in EER measurement) is about 50,000 L-mol ^"1 s ^"1 , more preferably about 25,000 L- mol ^"1 s ^"1 or less, and especially preferably about 10,000 L-mol ^'1 s ^"1 or less. Herein the EER is measured using the compound (XI) in a procedure (including temperature) described in Examples 21-23.

(XI) X=NorP

In these polymerizations it is preferred if the bidentate ligand is an α-diimine. It is also preferred if the oiefin has the formula R ¹⁷ CH=CH ₂ , wherein R ¹⁷ is hydrogen or n-alkyl.

In general for the polymers described herein, blends may be prepared with other polymers, and such other polymers may be elastomers, thermoplastics or thermosets . By elastomers are generally meant polymers whose Tg (glass transition temperature) and Tm (melting point) , if present, are below ambient temperature, usually considered to be about 20°C. Thermoplastics are those polymers whose Tg and/or Tm are at or above ambient temperature . Blends can be made by any of the common techniques known to the artisan, such as solution blending, or melt blending in a suitable apparatus such as a single or twin-screw extruder. Specific uses for the polymers of this application in the blends or as blends are listed below. Blends may be made with almost any kind of elastomer, such as EP, EPDM, SBR, natural rubber, polyisoprene, polybutadiene, neoprene, butyl rubber, styrene-butadiene block copolymers, segmented polyester-polyether copolymers, elastomeric polyurethanes, chlorinated or chlorosulfonated polyethylene, (per) fluorinated elastomers such as copolymers of vinylidene fluoride, hexafluoropropylene and optionally tetrafluoroethylene, copolymers of tetrafluoroethylene and perfluoro (methyl vinyl ether) , and copolymers of tetrafluoroethylene and propylene. Suitable thermoplastics which are useful for blending with the polymers described herein include: polyesters such as poly (ethylene terephthalate) , poly (butylene terephthalate) , and poly(ethylene

adipate) ; polyamides such as nylon-6, nylon-fa,b, ny on- 12, nylon-12,12, nylon-11, and a copolymer of hexamethylene diamine, adipic acid and terephthalic acid; fluorinated polymers such as copolymers of ethylene and vinylidene fluoride, copolymers of tetrafluoroethylene and hexafluoropropylene, copolymers of tetrafluoroethylene and a perfluoro(alkyl vinyl ether) such as perfluoro(propyl vinyl ether), and poly(vinyl fluoride); other halogenated polymers such a poly(vinyl chloride) and poly(vinylidene chloride) and its copolymers; polyolefins such as polyethylene, polypropylene and polystyrene, and copolymers thereof; (meth)acrylic polymers such a poly(methyl methacrylate) and copolymers thereof; copolymers of olefins such as ethylene with various (meth) acrylic monomers such as alkyl acrylates, (meth) crylic acid and ionomers thereof, and glycidyl (meth)acrylate) ; aromatic polyesters such as the copolymer of Bisphenol A and terephthalic and/or isophthalic acid; and liquid crystalline polymers such as aromatic polyesters or aromatic poly(ester-amides) .

Suitable ther osets for blending with the polymers described herein include epoxy resins, phenol- formaldehyde resins, melamine resins, and unsaturated polyester resins (sometimes called ther oset polyesters) . Blending with thermoset polymers will often be done before the thermoset is crosslinked, using standard techniques.

The polymers described herein may also be blended with uncrosslinked polymers which are not usually considered thermoplastics for various reasons, for instance their viscosity is too high and/or their melting point is so high the polymer decomposes below the melting temperature. Such polymers include poly(tetrafluoroethylene) , aramids such as poly(p- phenylene terephthalate) and poly(m-phenylene isophthalate) , liquid crystalline polymer such as

poly(benzoxazoles) , and non-melt processioie polyimides which are often aromatic polyimides.

All of the polymers disclosed herein may be mixed with various additives normally added to elastomers and thermoplastics [see EPSE (below) , vol. 14, p. 327-410] . For instance reinforcing, non-reinforcing and conductive fillers, such as carbon black, glass fiber, minerals such as clay, mica and talc, glass spheres, barium sulfate, zinc oxide, carbon fiber, and aramid fiber or fibrids, may be used. Antioxidants, antiozonants, pigments, dyes, delusterants, compounds to promote crosslinking may be added. Plasticizers such as various hydrocarbon oils may also be used. The following listing is of some uses for polyolefins, which are made from linear olefins and do not include polar monomers such as acrylates, which are disclosed herein. In some cases a reference is given which discusses such uses for polymers in general. All of these references are hereby included by reference. For the references, "U" refers to W. Gerhartz, et al . , Ed. , Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed. VCH Verlagsgesellschaft mBH, Weinheim, for which the volume and page number are given, "ECT3" refers to the H. F. Mark, et al . , Ed., Kirk-Othmer Encyclopedia of Chemical Technology, 4th Ed., John Wiley Sc Sons, New York, "ECT4" refers to the J. I Kroschwitz, et al . , Ed., Kirk-Othmer Encyclopedia of Chemical Technology, 4th Ed., John Wiley & Sons, New York, for which the volume and page number are given, "EPST" refers to H. F. Mark, et al . , Ed., Encyclopedia of Polymer Science and Technology, 1st Ed. , John Wiley & Sons, New York, for which the volume and page number are given, "EPSE" refers to H. F. Mark, et a . , Ed., Encyclopedia of Polymer Science and Engineering, 2nd Ed., John Wiley & Sons, New York, for which volume and page numbers are given, and "PM" refers to J. A. Brydson, ed., Plastics Materials, 5 Ed., Butterworth- Heinemann, Oxford, UK, 1989, and the page is given. In

these uses, a polyethylene, polypropylene and a copolymer of ethylene and propylene are preferred.

1. Tackifiers for low strength adhesives (U, vol. Al, p. 235-236) are a use for these polymers. Elastomeric and/or relatively low molecular weight polymers are preferred.

2. An oil additive for smoke suppression in single-stroke gasoline engines is another use. Elastomeric polymers are preferred. 3. The polymers are useful as base resins for hot melt adhesives (U, vol. Al, p. 233-234), pressure sensitive adhesives (U, vol. Al, p. 235-236) or solvent applied adhesives. Thermoplastics are preferred for hot melt adhesives. The polymers may also be used in a carpet installation adhesive.

4. Lubricating oil additives as Viscosity Index Improvers for multigrade engine oil (ECT3, Vol 14, p. 495-496) are another use. Branched polymers are preferred. Ethylene copolymer with acrylates or other polar monomers will also function as Viscosity Index

Improvers for multigrade engine oil with the additional advantage of providing some dispersancy.5. Polymer for coatings and/or penetrants for the protection of various porous items such as lumber and masonry, particularly out-of-doors. The polymer may be in a suspension or emulsion, or may be dissolved in a solvent .

6. Base polymer for caulking of various kinds is another use. An elastomer is preferred. Lower molecular weight polymers are often used.

7. The polymers may be grafted with various compounds particularly those that result in functional groups such as epoxy, carboxylic anhydride (for instance as with a free radically polymerized reaction with maleic anhydride) or carboxylic acid (EPSE, vol. 12, p. 445) . Such functionalized polymers are particularly useful as tougheners for various thermoplastics and thermosets when blended. When the

polymers are elastomers, the functional groups whicn are grafted onto them may be used as curesites to crosslink the polymers. Maleic anhydride-grafted randomly-branched polyolefins are useful as tougheners for a wide range of materials (nylon, PPO, PPO/styrene alloys, PET, PBT, POM, etc.) ; as tie layers in multilayer constructs such as packaging barrier films,- as hot melt, moisture-curable, and coextrudable adhesives; or as polymeric plasticizers . The maleic andhydride-graf ed materials may be post reacted with, for example; amines, to form other functional materials. Reaction with aminopropyl trimethoxysilane would allow for moisture-curable materials. Reactions with di- and tri-amines would allow for viscosity modifications.

8. The polymers, particularly elastomers, may be used for modifying asphalt, to improve the physical properties of the asphalt and/or extend the life of asphalt paving. 9. The polymers may be used as base resins for chlorination or chlorosulfonation for making the corresponding chlorinated or chlorosulfonated elastomers. The unchlorinated polymers need not be elastomers themselves. 10. Wire insulation and jacketing may be made from any of the polyolefins (see EPSE, vol. 17, p. 828- 842) . In the case of elastomers t may be preferable to crosslink the polymer after the insulation or jacketing is formed, for example by free radicals. 11. The polymers, particularly the elastomers, may be used as tougheners for other polyolefins such as polypropylene and polyethylene .

12. The base for synthetic lubricants (motor oils) may be the highly branched polyolefins described herein (ECT3, .vol. 14, p. 496-501) .

13. The branched polyolefins herein can be used as drip suppressants when added to other polymers.

14. The branched polyolefins herein are especially useful in blown film applications because of their particular rheological properties (EPSE, vol. 7, p. 88-106) . It is preferred that these polymers have some crystallinity.

15. The polymer described herein can be used to blend with wax for candles, where they would provide smoke suppression and/or drip control.

16. The polymers, especially the .branched polymers, are useful as base resins for carpet backing, especially for automobile carpeting.

17. The polymers, especially those which are relatively flexible, are useful as capliner resins for carbonated and noncarbonated beverages. 18. The polymers, especially those having a relatively low melting point, are useful as thermal transfer imaging resins (for instance for imaging tee- shirts or signs) .

19. The polymers may be used for extrusion or coextrusion coatings onto plastics, metals, textiles or paper webs.

20. The polymers may be used as a laminating adhesive for glass.

21. The polymers are useful as for blown or cast films or as sheet (see EPSE, vol. 7 p. 88-106;

ECT4, vol. 11, p. 843-856; PM, p. 252 and p. 432ff) . The films may be single layer or multilayer, the multilayer films may include other polymers, adhesives, etc. For packaging the films may be stretch-wrap, shrink-wrap or cling wrap. The films are useful form many applications such as packaging foods, geomembranes and pond liners. It is preferred that these polymers have some crystallinity.

22. The polymers may be used to form flexible or rigid foamed objects, such as cores for various sports items such as surf boards and liners for protective headgear. Structural foams may also be made. It is preferred that the polymers have some

crystallinity. The polymer of the foams may be crosslinked.

23. In powdered form the polymers may be used to coat objects by using plasma, flame spray or fluidized bed techniques.

24. Extruded films may be formed from these polymers, and these films may be treated, for example drawn. Such extruded films are useful for packaging of various sorts . 25. The polymers, especially those that are elastomeric, may be used in various types of hoses, such as automotive heater hose.

26. The polymers, especially those that are branched, are useful as pour point depressants for fuels and oils.

27. These polymers may be flash spun to nonwoven fabrics, particularly if they are crystalline

(see EPSE vol. 10, p. 202-253) They may also be used to form spunbonded polyolefins (EPSE, vol. 6, p. 756- 760) . These fabrics are suitable as house wrap and geotextiles.

28. The highly branched, low viscosity polyolefins would be good as base resins for master- batching of pigments, fillers, flame-retardants, and related additives for polyolefins. 29. The polymers may be grafted with a compound containing ethylenic unsaturation and a functional group such as a carboxyl group or a derivative of a carboxyl group, such as ester, carboxylic anhydride of carboxylate salt. A minimum grafting level of about 0.01 weight percent of grafting agent based on the weight of the grafted polymer is preferred. The grafted polymers are useful as compatibilizers and/or tougheners. Suitable grafting agents include maleic, acrylic, methacrylic, itaconic, crotonic, alpha-methyl crotonic and cinnamic acids, anhydrides, esters and their metal salts and fumaric acid and their esters, anhydrides (when appropriate) and metal salts.

Copolymers of linear olefins with 4- vinylcyclohexene and other dienes may generally be used for all of the applications for which the linear olefins polymers (listed above) may be used. In addition they may be sulfur cured, so they generally can be used for any use for which EPDM polymers are used, assuming the olefin/4-vinylcyclohexene polymer is elastomeric.

Also described herein are novel copolymers of linear olefins with various polar monomers such as acrylic acid and acrylic esters. Uses for these polymers are given below. Abbreviations for references describing these uses in general with polymers are the same as listed above for polymers made from linear olefins.

1. Tackifiers for low strength adhesives (U, vol. Al, p. 235-236) are a use for these polymers. Elastomeric and/or relatively low molecular weight polymers are preferred. 2. The polymers are useful as base resins for hot melt adhesives (U, vol. Al, p. 233-234), pressure sensitive adhesives (U, vol. Al, p. 235-236) or solvent applied adhesives. Thermoplastics are preferred for hot melt adhesives. The polymers may also be used in a carpet installation adhesive.

3. Base polymer for caulking of various kinds is another use. An elastomer is preferred. Lower molecular weight polymers are often used.

4. The polymers, particularly elastomers, may be used for modifying asphalt, to improve the physical properties of the asphalt and/or extend the life of asphalt paving, see U.S. patent 3,980,598.

5. Wire insulation and jacketing may be made from any of the polymers (see EPSE, vol. 17, p. 828- 842) . In the case of elastomers it may be preferable to crosslink the polymer after the insulation or jacketing is formed, for example by free radicals.

6. The polymers, especially the branched polymers, are useful as base resins for carpet backing, especially for automobile carpeting.

7. The polymers may be used for extrusion or coextrusion coatings onto plastics, metals, textiles or paper webs .

8. The polymers may be used as a laminating adhesive for glass.

9. The polymers are useful as for blown or cast films or as sheet (see EPSE, vol. 7 p. 88-106; ECT4 , vol. 11, p. 843-856; PM, p. 252 and p. 432ff) . The films may be single layer or multilayer, the multilayer films may include other polymers, adhesives, etc. For packaging the films may be stretch-wrap, shrink-wrap or cling wrap. The films are useful form many applications such as packaging foods, geomembranes and pond liners. It is preferred that these polymers have some crystallinity.

10. The polymers may be used to form flexible or rigid foamed objects, such as cores for various sports items such as surf boards and liners for protective headgear. Structural foams may also be made. It is preferred that the polymers have some crystallinity. The polymer of the foams may be crosslinked.

11. In powdered form the polymers may be used to coat objects by using plasma, flame spray or fluiaized bed techniques.

12. Extruded films may be formed from these polymers, and these films may be treated, for example drawn. Such extruded films are useful for packaging of various sorts.

13. The polymers, especially those that are elastomeric, may be used in various types of hoses, such as automotive heater hose.

14. The polymers may be used as reactive diluents in automotive finishes, and for this purpose

.30

it is preferred that they have a relatively low molecular weight and/or have some crystallinity.

15. The polymers can be converted to ionomers, which when the possess crystallinity can be used as molding resins. Exemplary uses for these ionomeric molding resins are golf ball covers, perfume caps, sporting goods, film packaging applications, as tougheners in other polymers, and usually extruded) detonator cords. 16. The functional groups on the polymers can be used to initiate the polymerization of other types of monomers or to copolymerize with other types of monomers. If the polymers are elastomeric, they can act as toughening agents. 17. The polymers can act as compatibilizing agents between various other polymers.

18. The polymers can act as tougheners for various other polymers, such as thermoplastics and thermosets, particularly if the olefin/polar monomer polymers are elastomeric.

19. The polymers may act as internal plasticizers for other polymers in blends. A polymer which may be plasticized is poly(vinyl chloride) .

20. The polymers can serve as adhesives between other polymers.

21. With the appropriate functional groups, the polymers may serve as curing agents for other polymers with complimentary functional groups (i.e., the functional groups of the two polymers react with each other) .

22. The polymers, especially those that are branched, are useful as pour point depressants for fuels and oils.

23. Lubricating oil additives as Viscosity Index Improvers for multigrade engine oil (ECT3, Vol

14, p. 495-496) are another use. Branched polymers are preferred. Ethylene copolymer with acrylates or other polar monomers will also function as Viscosity Index

Improvers for multigrade engine oil with the additional advantage of providing some dispersancy.

24. The polymers may be used for roofing membranes.

25. The polymers may be used as additives to various molding resins such as the so-called thermoplastic olefins to improve paint adhesion, as in automotive uses. Polymers with or without polar monomers present are useful in the following uses. Preferred polymers with or without polar monomers are those listed above in the uses for each "type" .

1. A flexible pouch made from a single layer or multilayer film (as described above) which may be used for packaging various liquid products such as milk, or powder such as hot chocolate mix. The pouch may be heat sealed. It may also have a barrier layer, such as a metal foil layer. 2. A wrap packaging film having differential cling is provided by a film laminate, comprising at least two layers; an outer reverse which is a polymer (or a blend thereof) described herein, which contains a tackifier in sufficent amount to impart cling properties; and an outer obverse which has a density of at least about 0.916 g/mL which has little or no cling, provided that a density of the outer reverse layer is at least 0.008 g/mL less than that of the density of the outer obverse layer. It is preferred that the outer obverse layer is linear low density polyethylene, and the polymer of the outer obverse layer have a density of less than 0.90 g/mL. All densities are measured at 25°C.

3. Fine denier fibers and/or multifilaments . These may be melt spun. They may be in the form of a filament bundle, a non-woven web, a woven fabric, a knitted fabric or staple fiber.

4. A composition comprising a mixture of the polymers herein and an antifogging agent. This composition is especially useful in film or sheet form because of its antifogging properties. 5. Elastic, randomly-branched oiefin polymers are disclosed which have very good processability, including processing indices (Pi's) less than or equal to 70 percent of those of a comparative linear oiefin polymer and a critical shear rate at onset of surface melt fracture of at least 50 percent greater than the critical shear rate at the onset of surface melt fracture of a traditional linear oiefin polymer at about the same 12 and Mw/Mn. The novel polymers may have higher low/zero shear viscosity and lower high shear viscosity than comparative linear oiefin polymers made by other means. These polymers may be characterized as having: a) a melt flow ratio, 110/12, > 5.63, b) a molecular weight distribution, Mw/Mn, defined by the equation: Mw/Mn ≤ (110/12) -4.63, and c) a critical shear rate at onset of surface melt fracture of at least 50 percent greater than the critical shear rate at the onset of surface melt fracture of a linear oiefin polymer having about the same 12 and Mw/Mn. Some blends of these polymer are characterized as having: a) a melt flow ratio, 110/12, > 5.63, b) a molecular weight distribution, Mw/Mn, defined by the equation: Mw/Mn ≤ (110/12) -4.63, and c) a critical shear rate at onset of surface melt fracture of at least 50 percent greater than the critical shear rate at the onset of surface melt fracture of a linear oiefin polymer having about the same 12 and Mw/Mn and (b) at least one other natural or synthetic polymer chosen from the polymer of claims 1, 3, 4, 6, 332, or 343, a conventional high density polyethylene, low density polyethylene or linear low density polyethylene polymer. The polymers may be further characterized as having a melt flow ratio, 110/12, > 5.63, a molecular weight distribution, Mw/Mn, defined by the equation:

Mw/Mn < (110/12) -4.63 , and a critical shear stress at onset of gross melt fracture of greater than about 400 kPa (4x10 dyne/cm ) and their method of manufacture are disclosed. The randomly-branched oiefin polymers preferably have a molecular weight distribution from about 1.5 to about 2.5. The polymers described herein often have improved processability over conventional oiefin polymers and are useful in producing fabricated articles such as fibers, films, and molded parts. For this paragraph, ^' the value 12 is measured in accordance with ASTM D-1238-190/2.16 and 110 is measured in accordance with ASTM D-1238-190/10; critical shear rate at onset of surface melt fracture and processing index (PI) are defined in U.S. Patent 5,278,272, which is hereby included by reference.

In another process described herein, the product of the process described herein is an α-olefin. It is preferred that in the process a linear α-olefin is produced. It is also preferred that the α-olefin contain 4 to 32, preferably 8 to 20, carbon atoms.

(XXXI)

When (XXXI) is used as a catalyst, a neutral Lewis acid or a cationic Lewis cr Bronsted acid whose counterion is a weakly coordinating anion is also present as part of the catalyst system (sometimes called a "first compound" in the claims) .. By a "neutral Lewis acid" is meant a compound which is a Lewis acid capable for abstracting X ^" from (I) to form a weakly coordinating anion. The neutral Lewis acid is originally uncharged (i.e., not ionic) . Suitable neutral Lewis acids include SbF ₅ , Ar ₃ B (wherein Ar is

aryl) , and BF ₃ . By a cationic Lewis acid is meant- a cation with a positive charge such as Ag ^* , H ⁺ , and Na ^* .

A preferred neutral Lewis acid is an alkyl aluminum compound, such as R ⁹ ₃ A1, R ⁹ ₂ A1C1, R ⁹ A1C1 ₂ , and "R ⁹ A10" (alkylaluminoxane) , wherein R ⁹ is alkyl containing 1 to 25 carbon atoms, preferably 1 to 4 carbon atoms. Suitable alkyl aluminum compounds include methylaluminoxane, (C ₂ H _s ) ₂ AlCl, C ₂ H ₅ A1C1 ₂ , and [(CH ₃ ) ₂ CHCH ₂ ] ₃ A1. Relatively noncoordinating anions are known in the art, and the coordinating ability of such anions is known and has been discussed in the literature, 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. Among such anions are those formed from the aluminum compounds in the immediately preceding paragraph and X ^" , including R ⁹ ₃ A1X ^" , R ⁹ ₂ A1C1X ^" , R ⁹ A1C1 ₂ X ^" , and "R ⁹ A10X ^" " . Other useful noncoordinating anions include BAF ^* (BAF = tetrakis [3, 5- bis (trifluoromethyl)phenyl]borate} , SbF ₆ ^" , PF ₆ ^" , and BF ₄ ^" , trifluoromethanesulfonate, p-toluenesulfonate, (R _f S0 ₂ ) ₂ N ^" , and (C ₆ F _S ) ₄ B ^* .

The temperature at which the process is carried out is about -100°C to about +200°C, preferably about 0°C to about 150°C, more preferably about 25°C to about 100°C. It is believed that at higher temperatures, lower molecular weight α-olefins are produced, all other factors being equal. The pressure at which the polymerization is carried out is not critical, atmospheric pressure to about 275 MPa being a suitable range. It is also believed that increasing the pressure increases the relative amount of α-olefin (as opposed to internal oiefin) produced. The process to make α-olefins may be run in a solvent (liquid) , and that is preferred. The solvent may in fact be the α-olefin produced. Such a process may be started by using a deliberately added solvent

which is gradually displaced as tne reaction proceeds. By solvent it is not necessarily meant that any or all of the starting materials and/or products are soluble in the (liquid) solvent.

In (I) it is preferred that R ³ and R ⁴ are both hydrogen or methyl or R ³ and R ⁴ taken together are

(An) It is also preferred that each of Q and S is independently chlorine or bromine, and it is more preferred that both of Q and S in (XXXI) are chlorine or bromine.

In (XXXI) R ² and R ⁵ are hydrocarbyl or substituted hydrocarbyl. What these groups are greatly determines whether the α-olefins of this process are made, or whether higher polymeric materials, i.e., materials containing over 25 ethylene units, are coproduced or produced almost exclusively. If R ^* and R are highly sterically hindered about the nickel atom, the tendency is to produce higher polymeric material. For instance, when R ^" and R are both 2 , 6-diisopropylphenyl mostly higher polymeric material is produced. However, when R ^" and R are both phenyl, mostly the α-olefins of this process are produced. Of course this will also be influenced by other reaction conditions such as temperature and pressure, as noted above. Useful groups for R' and R ⁵ are phenyl, and p-methylphenyl . As is understood by the artisan, in oligomerization reactions of ethyiene to produce α- olefins, usually a mixture of such α-olefins is obtained containing a series of such α-olefins differing from one another by two carbon atoms (an ethylene unit) . The process for preparing α-olefins described herein produces products with a high

percentage of terminal olefinic groups (as opposed to internal olefinic groups) . The product mixture also contains a relatively high percentage of molecules which are linear. Finally relatively high catalyst efficiencies can be obtained.

The α-olefins described as being made herein may also be made by contacting ethylene with one of the compounds

( I I I ) or

(XXXIV)

wherein R ² , R ³ , R ⁴ , and R ⁵ are as defined (and preferred) as described above (for the preparation of α -olefins) , and T ¹ is hydrogen or n-alkyl containing up to 38 carbon atoms, Z is a neutral Lewis base wherein the donating atom is nitrogen, sulfur, or oxygen, provided that if the donating atom is nitrogen then the pKa of the conjugate acid of that compound (measured in water) is less than about 6, U is n-alkyl containing up to 38 carbon atoms, and X is a noncoordinating anion (see above) . The process conditions for making α- olefins using (III) or (XXXIV) are the same as for using (XXXI) to make these compounds except a Lewis or Bronsted acid need not be present. Note that the double line in (XXXIV) represents a coordinated

ethylene molecule. (XXXIV) may be made""from (II) by reaction of (III) with ethylene. In other words, (XXXIV) may be considered an active intermediate in the formation of α-olefin from (III) . Suitable groups for Z include dialkyl ethers such as diethyl ether, and alkyl nitriles such as acetonitrile.

In general, α-olefins can be made by this process using as a catalyst a Ni [II] complex of an α-diimine of formula (VIII) , wherein the Ni[II] complex is made by any of the methods which are described above, using

Ni [0] , Ni[I] or Ni [II] precursors. All of the process conditions, and preferred groups on (VIII) , are the same as described above in the process for making α- olefins .

EXAMPLES In the Examples, the following convention is used for naming α-diimine complexes of metals, and the α- diimine itself. The α-diimine is indicated by the letters "DAB" . To the left of the "DAB" are the two groups attached to the nitrogen atoms, herein usually called R ² and R ^s . To the right of the "DAB" are the groups on the two carbon atoms of the α-diimine group, herein usually termed R ³ and R ⁴ . To the right of all this appears the metal, ligands attached to the metal

(such as Q, S and T) , and finally any anions (X) , which when "free" anions are designated by a superscript minus sign (i.e., X ^" ) . Of course if there is a "free" anion present, the metal containing moiety is cationic. Abbreviations for these groups are as described in the Specification in the Note after Table 1. Analogous abbreviations are used for α-diimines, etc.

In the Examples, the following abbreviations are used: ΔH - heat of fusion acac - acetylacetonate

Bu - butyl t-BuA - t-butyl acrylate

DMA - Dynamic Mechanical Analysis

DME - 1, 2-dimethoxyethane

DSC - Differential Scanning Calorimetry

E - ethylene EOC - end of chain

Et - ethyl

FC-75 - perfluoro (n-butyltetrahydrofuran)

FOA - fluorinated octyl acrylate

GPC - gel permeation chromatography MA - methyl acrylate

MAO - methylaluminoxane

Me - methyl

MeOH - methanol

MMAO - a modified methylaluminoxane in which about 25 mole percent of the methyl groups have been replaced by isobutyl groups

M-MAO - see MMAO

MMAO-3A - see MMAO

Mn - number average molecular weight MVK - methyl vinyl ketone

Mw- weight average molecular weight

Mz - viscosity average molecular weight

PD or P/D - polydispersity, Mw/Mn

Ph - phenyl PMAO - see MAO

PMMA - poly(methyl methacrylate)

Pr - propyl

PTFE - polytetrafluoroethylene

RI - refractive index RT (or rt) - room temperature

TCE - 1, 1, 2,2-tetrachloroethane

Tc - temperature of crystallization

Td - temperature of decomposition

Tg - glass transition temperature TGA - Thermogravimetric Analysis

THF - tetrahydrofuran

Tm - melting temperature

TO - turnovers, the number of mo*? ^" !^ *6 πϊbflomer ^' polymerized per g-atom of metal in the catalyst used UV - ultraviolet Unless otherwise noted, all pressures are gauge pressures .

In the Examples, the following procedure was used to quantitatively determine branching, and the distribution of branch sizes in the polymers (but not necessarily the simple number of branches as measured by total number of methyl groups per 1000 methylene groups) . 100 MHz ¹³ C NMR spectra were obtained on a Varian Unity 400 MHz spectrometer using a 10 mm probe on typically 15-20 wt% solutions of the polymers and 0.05 M Cr (acetylacetonate) ₃ in 1, 2, 4-trichlorobenzene (TCB) unlocked at 120-140°C using a 90 degree pulse of 12.5 to 18.5 μsec, a spectral width of 26 to 35 kHz, a relaxation delay of 5-9 s, an acquisition time of 0.64 sec and gated decoupling. Samples were preheated for at least 15 min before acquiring data. Data acquisition time was typically 12 hr. per sample. The T ¹ values of the carbons were measured under these conditions to be all less than 0.9 s. The longest T ¹ measured was for the Bu ⁺ , end of chain resonance at 14 ppm, which was 0.84 s. Occasionally about 16 vol. % benzene-d _€ was added to the TCB and the sample was run locked. Some samples were run in chloroform-dl, CDC1 ₃ - dl, (locked) at 30°C under similar acquisition parameters. T ¹ ' s were also measured in CDC1 ₃ at ambient temperature on a typical sample with 0.05 M Cr (acetylacetonate) ₃ to be all less than 0.68 s. In rare cases when Cr (acetylacetonate) ₃ was not used, a 30-40 s recycle delay was used to insure quantitation. The giycidyl acrylate copolymer was run at 100°C with Cr (acetylacetonate) ₃ . Spectra are referenced to the solvent - either the TCB highfield resonance at 127.8 ppm or the chloroform-dl triplet at 77 ppm. A DEPT 135 spectrum was done on most samples to distinguish methyls and methines from methylenes . Methyls were

.iistinguished from methines by chemical shift. EOC is end-of-chain. Assignments reference to following naming scheme:

1. xBy: By is a branch of length y carbons; x is the carbon being discussed, the methyl at the end of the branch is numbered 1. Thus the second carbon from the end of a butyl branch is 2B4. Branches of length y or greater are designated as y ⁺ .

2. xEBy: EB is an ester ended branch containing y methylenes. x is the carbon being discussed, the first methylene adjacent to the ester carbonyl is labeled 1. Thus the second methylene from the end of a 5 methylene ester terminated branch would be 2EB5. ¹³ C NMR of model compounds for EBy type branches for y=0 and y=5 ⁺ confirm the peak positions- and assignments of these branches. In addition, a model compound for an EB1 branch is consistent with 2 dimensional NMR data using the well know 2D NMR techniques of hsqc, hmbc, and hsqc-tocsy; the 2D data confirms the presence of the EB5 ⁺ , EBO, EB1 and other intermediate length EB branches

3. The methylenes in the backbone are denoted with Greek letters which determine how far from a branch point methine each methylene is. Thus ββ (beta beta) B denotes the central methylene in the following PCHRCH2CH CH HRP. Methylenes that are three or more carbons from a branch point are designated as γ ⁺ (gamma ⁺ ) .

4. When x in xBy or xEBy is replaced by a M, the methine carbon of that branch is denoted.

Integrals of unique carbons in each branch were measured and were reported as number of branches per 1000 methylenes (including methylenes in the backbone and branches) . These integrals are accurate to +/- 5% relative for abundant branches and +/- 10 or 20% relative for branches present at less than 10 per 1000 methylenes.

141

Such types of analyses are generally -Known, see for instance "A Quantitative Analysis of Low Density (Branched) Polyethylenes by Carbon-13 Fourier Transform Nuclear Magnetic Resonance at 67.9 MHz", D. E. Axelson, et al . , Macromolecules 12 (1979) pp. 41-52; "Fine Branching Structure in High-Pressure, Low Density Polyethylenes by 50.10-MHz 13C NMR Analysis", T. Usami et al . , Macromolecules 17 (1984) pp. 1757-1761; and "Quantification of Branching in Polyethylene by 13C NMR Using Paramagnetic Relaxation Agents", J. V. Prasad, et al., Eur. Polym. J. 27 (1991) pp. 251-254 (Note that this latter paper is believed to have some significant, typographical errors in it) .

It is believed that in many of the polymers described herein which have unusual branching, i.e., they have more or fewer branches than would be expected for "normal" coordination polymerizations, or the distribution of sizes of the branches is different from that expected, that "branches on branches" are also present. By this is meant that a branch from the main chain on the polymer may itself contain one or more branches. It is also noted that the concept of a "main chain" may be a somewhat semantic argument if there are sufficient branches on branches in any particular polymer.

By a polymer hydrocarbyl branch is meant a methyl group to a methine or quaternary carbon atom or a group of consecutive methylenes terminated at one end by a methyl group and connected at the other end to a methine or quaternary carbon atom. The length of the branch is defined as the number of carbons from and including the methyl group to the nearest methine or quaternary carbon atom, but not including the methine or quaternary carbon atom. If the number of consecutive methylene groups is "n" then the branch contains (or the branch length is) n+1. Thus the structure (which represents part of a polymer) -

H ₂ CH ₂ CH[CH ₂ CH ₂ CH ₂ CH ₂ CH(CH ₃ )CH ₂ CH ₃ ]CH ₂ CH ₂ CH ₂ CH ₂ - contains 2 branches, a methyl and an ethyl branch.

For ester ended branches a similar definition is used. An ester branch refers to a group of consecutive methylene groups terminated at one end by an ester -

COOR group, and connected at the other end to a methine or quaternary carbon atom. The length of the branch is defined as the number of consecutive methylene groups from the ester group to the nearest methine or quaternary carbon atom, but not including the methine or quaternary carbon atom. If the number of methylene groups is "n" , then the length of the branch is n. Thus -CH ₂ CH ₂ CH[CH ₂ CH ₂ CH ₂ CH ₂ CH(CH ₃ )CH ₂ C00R] CH ₂ CH ₂ CH ₂ CH ₂ - contains 2 branches, a methyl and an n=l ester branch. The ¹³ C NMR peaks for .copolymers of cyclopentene and ethylene are described based on the labeling scheme and assignments of A. Jerschow et al, Macromolecules 1995, 28 , 7095-7099. The triads and pentads are described as 1-cme, 1,3-ccmcc, 1,3-cmc, 2-cme, 2-cmc, 1, 3-eme, 3-cme, and 4,5-cmc, where e = ethylene, c = cyclopentene, and m = meta cyclopentene (i.e. 1,3 enchainment) . The same labeling is used for cyclopentene/l-pentene copolymer substituting p = pentene for e. The synthesis of diimines is reported in the literature (Tom Dieck, H. ,- Svoboda, M.; Grieser, T. Z. Naturforsch 1981, 36 ^" Jb, 823-832. Kliegman, J. M.; Barnes, R. K. J. Org . Chem. 1970, 35, 3140-3143.)

Example 1

[ (2, 6-i-PrPh) ₂ DABMe ₂ ] PdMeCl Et ₂ 0 (75 mL) was added to a Schlenk flask containing CODPdMeCl (COD = 1, 5-cyclooctadiene) (3.53 g, 13.3 mmol) and a slight excess of (2,6-i- PrPh) ₂ DABMe ₂ (5.43 g, 13.4 mmol, 1.01 equiv) . An orange precipitate began to form immediately upon mixing. The reaction mixture was stirred overnight and the Et ₂ 0 and free COD were then removed via filtration. The product was washed with an additional 25 mL of Et ₂ 0 and then dried overnight in vacuo. A pale orange

powder (7.18 g, 95.8%) was isolated: ¹ H NMR (CD ₂ C1 ₂ , 400 MHz) δ 7.4 - 7.2 (m, 6, H _ary ι) , 3.06 (septet, 2, J = 6.81, CHMe ₂ ) , 3.01 (septet, 2, J = 6.89, C'flMe ₂ ) , 2.04 and 2.03 (N=C (Me) -C (Me) =N) , 1.40 (d, 6, J = 6.79, C'HMeMe ¹ ) , 1.36 (d, 6, J = 6.76, CHMeMe ' ) , 1.19 (d, 6, J = 6.83, CHMeMe') , 1.18 (d, 6, J = 6.87, C'HMeMe') , 0.36 (s, 3, PdMe) ; ¹³ C NMR (CD ₂ C1 ₂ , 400 MHz) δ 175.0 and 170.3 (N=C-C'=N) , 142.3 and 142.1 (Ar, Ar ' : C _ιpso ) , 138.9 and 138.4 (Ar, Ar ' : C ₀ ) , 128.0 and 127.1 (Ar, Ar' : C _p ) , 124.3 and 123.5 (Ar, Ar ' : C _m ) , 29.3 (CHMe ₂ ) , 28.8 (C'HMe ₂ ) , 23.9, 23.8, 23.5 and 23.3 (CHMeMe', C'HMeMe') , 21.5 and 20.1 (N=C (Me) -C ' (Me) =N) , 5.0 (J _CH = 135.0, PdMe) .

Example 2 [ (2, 6-i-PrPh) ₂ DABH ₂ ] PdMeCl Following the procedure of Example 1, an orange powder was isolated in 97.1% yield: ^" -H NMR (CD ₂ C1 ₂ , 400 MHz) δ 8.31 and 8.15 (s, 1 each, N=C (H) -C' (H) =N) , 7.3 - 7.1 (m, 6, H _ary ι) , 3.22 (septet, 2, J = 6.80, C«Me ₂ ) , 3.21 (septet, 2, J = 6.86, C'HMe ₂ ) , 1.362, 1.356, 1.183 and 1.178 (d, 6 each, J = 7.75 - 6.90; CHMeMe ' , C'HMeMe ') , 0.67 (s, 3, PdMe) ; ¹³ C NMR (CD ₂ C1 ₂ , 100 MHz) δ 164.5 (J _C H = 179.0, N-C(H) ) , 160.6 (JCH = 178.0, N=C'(H)) , 144.8 and 143.8 (Ar, Ar' : ipso) - 140.0 and 139.2 (Ar, Ar' : C ₀ ) , 128.6 and 127.7 (Ar, Ar' : C _p ) , 124.0 and 123.4 (Ar, Ar' : C _m ) , 29.1 (CHMe ₂ ) , 28.6 (C'HMe ₂ ) , 24.7, 24.1, 23.1 and 22.7 (CHMeMe ' , C*HMeMe ' ) , 3.0 (J _C H = 134.0, PdMe) . Anal . Calcd for (C ₂₇ H ₃₉ ClN ₂ Pd) : C, 60.79; H, 7.37; N, 5.25. Found: C, 60.63; H, 7.24; N, 5.25.

Example 3 [ (2,6-MePh) ₂ DABMe ₂ ]PdMeCl Following the procedure of Example 1, a yellow powder was isolated in 90.6% yield: ^" -H NMR (CD ₂ C1 ₂ , 400 MHz) δ 7.3 - 6.9 (m, 6, H _ary ι) , 2.22 (s, 6, Ar, Ar' Me) , 2.00 and 1.97 (N=C(Me) -C' (Me) =N) , 0.25 (s, 3, PdMe) . Example 4

[ (2,6-MePh) ₂ DABMe ₂ ] PdMeCl Following the procedure of Example 1, an orange powder was isolated in 99.0% yield: ^" -H NMR (CD ₂ C1 ₂ , 400 MHz, 41 °C) δ 8.29 and 8.14 (N=C ( H) -C (H) =N) , 7.2 - 7.1 (m, 6, H _ary ι) , 2.33 and 2.30 (s, 6 each, Ar, Ar' : Me) , 0.61 (s, 3, PdMe) ; ¹³ C NMR (CD ₂ C1 ₂ , 100 MHz, 41 °C) δ 165.1 (JCH = 179.2, N=C(H) ) , 161.0 ^' (J _CH = 177.8 (N=C (H) ) , 147.3 and 146.6 (Ar, Ar' : Ci _pso ) , 129.5 and 128.8 (Ar, Ar' : C _σ ) , 128.8 and 128.5 (Ar, Ar' : C _m ) , 127.9 and 127.3 (Ar, Ar' : C _p ) , 18.7 and 18.2 (Ar, Ar ' : Me) , 2.07 (J _CH = 136.4, PdMe) .

Example 5 [4-MePh) ₂ DABMe ₂ ] PdMeCl Following the procedure of Example 1, a yellow powder was isolated in 92.1% yield: ^" -H NMR (CD ₂ C1 ₂ , 400 MHz) δ 7.29 (d, 2, J = 8.55, Ar: Hπ,) , 7.26 (d, 2, J = 7.83, Ar' : Ha,) , 6.90 (d, 2, J = 8.24, Ar ¹ : H ₀ ) , 6.83 (d, 2, J = 8.34, Ar: H ₀ ) , 2.39 (s, 6, Ar, Ar' : Me) , 2.15 and 2.05 (s, 3 each, N=C(Me) -C (Me) =N) , 0.44 (s, 3, PdMe) ; ^'13 C NMR (CD ₂ C1 ₂ , 100 MHz) δ 176.0 and 169.9 (N=C-C'=N) , 144.9 and 143.7 (Ar, Ar' : C _ipso ) , 137.0 and 136.9 (Ar, Ar' : C _p ) , 130.0 and 129.3 (Ar, Ar' : C _m ) , 122.0 and 121.5 (Ar, Ar' : C _σ ) , 21.2 (N=C(Me)) , 20.1 (Ar, Ar' : Me) , 19.8 (N=C' (Me) ) , 2.21 (J _CH = 135.3, PdMe) . Anal. Calcd for (C ₁₉ H ₂₃ ClN ₂ Pd) : C, 54.17; H, 5.50; N, 6.65. Found: C, 54.41; H, 5.37; N, 6.69.

Example 6

[ (4-MePh) ₂ DABH ₂ ] PdMeCl Following the procedure of Example 1, a burnt orange powder was isolated in 90.5% yield: Anal. Calcd for (Cι ₇ H ₁₉ ClN ₂ Pd) : C, 51.93; H, 4.87; N, 7.12. Found: C, 51.36; H, 4.80; N, 6.82.

Example 7

({ [ (2,6-i-PrPh) ₂ DABMe ₂ ] PdMe} ₂ (μ-Cl))BAF" Et ₂ 0 (25 mL) was added to a mixture of [(2,6-i- PrPh) ₂ DABMe ₂ ] PdMeCl (0.81 g, 1.45 mmol) and 0.5 equiv of NaBAF (0.64 g, 0.73 mmol) at room temperature. A golden yellow solution and NaCI precipitate formed immediately upon mixing. The reaction mixture was stirred overnight and then filtered. After the Et ₂ 0 was removed in vacuo, the product was washed with 25 mL of hexane . The yellow powder was then dissolved in 25 mL of CH ₂ C1 ₂ and the resulting solution was filtered in order to removed traces of unreacted NaBAF. Removal of CH ₂ C1 in vacuo yielded a golden yellow powder (1.25 g, 88.2%) : ^" -H NMR (CD ₂ C1 ₂ , 400 MHz) δ 7.73 (s, 8, BAF: H ₀ ) , 7.57 (s, 4; BAF: H _p ) , 7.33 (t, 2, J = 7.57, Ar: U _p ) , 7.27 (d, 4, J = 7.69, Ar: H ₀ ) , 7.18 (t, 2, J = 7.64, Ar: H _p ) , 7.10 (d, 4, J = 7.44, Ar' : H _D ) , 2.88

(septet, 4, J = 6.80, CflMe ₂ ) , 2.75 (septet, 4, J = 6 82, C'HMe ₂ ) , 2.05 and 2.00 (s, 6 each, N=C(Me)- C' (Me)=N) , 1.22, 1.13, 1.08 and 1.01 (d, 12 each, J = 6.61-6.99, CHMeMe', C'HMeMe') , 0.41 (s, 6, PdMe) ; ¹³ C NMR (CD ₂ C1 ₂ , 100 MHz) δ 177.1 and 171.2 (N=C-C'=N) ,

162.2 (q, J _B c - 49.8, BAF: Ci _pso ) , 141.4 and 141.0 (Ar, Ar' : Cipso) , 138.8 and 138.1 (Ar, Ar ¹ : C _D ) , 135.2 (BAF: C _p ) , 129.3 (q, JCF = 31.6, BAF: C _m ) , 128.6 and 127.8 (Ar, Ar' : C _p ) , 125.0 (q, J _C F = 272.5, BAF: CF ₃ ) , 124.5 and 123.8 (Ar, Ar* : C _m ) , 117.9 (BAF: C _p ) , 29.3 (CHMe ₂ ) , 29.0 (C'HMe ₂ ) , 23.8, 23.7, 23.6 and 23.0 (CHMeMe', C'HMeMe') , 21.5 and 20.0 (N=C (Me) -C (Me) =N) , 9.8 (JCH = 136.0, PdMe) . Anal. Calcd for (C ₉ oH9 ₈ BClF24N ₄ Pd2) : C, 55.41; H, 5.06; N, 2.87. Found: C, 55.83; H, 5.09; N, 2.63.

Example 8 <{ [ (2, 6-i-PrPh) ₂ DABH ₂ ] PdMe} ₂ (μ-Cl) >BAF ^" The procedure of Example 7 was followed with one exception, the removal of CH ₂ C1 ₂ in vacuo yielded a product that was partially an oil. Dissolving the compound in Et ₂ 0 and then removing the Et ₂ 0 in vacuo yielded a microcrystalline red solid (85.5%) : ^" -H NMR (CD ₂ C1 ₂ , 400 MHz) δ 8.20 and 8.09 (s, 2 each, N=C(H)- C' (H)=N) , 7.73 (S, 8, BAF: H ₀ ) , 7.57 (s, 4, BAF: H _p ) , 7.37 (t, 2, J = 7.73, Ar : H _p ) , 7.28 (d, 4, J = 7.44, Ar: Hrn) , 7.24 (t, 2, Ar ' : H _p ) , 7.16 (d, 4, J = 7.19, Ar' : Hrn) , 3.04 (septet, 4, J = 6.80, CJiMe ) , 2.93 (septet, 4, J = 6.80, C'HMe ₂ ) , 1.26 (d, 12, J = 6.79, CHMeMe') , 1.14 (d, 12, J = 6.83, CHMeMe') , 1.11 (d, 12, J = 6.80, C'HMeMe') , 1.06 (d, 12, J = 6.79, C'HMeMe') , 0.74 (s, 6, PdMe) ; ¹³ C NMR (CD ₂ C1 ₂ , 100 MHz) δ 166.0 (JCH = 180.4, N=C(H) ) , 161.9 (q, J _B c = 49.6, BAF: Cipso) , 160.8 (JCH = 179.9, N=C (H) ) , 143.5 and 143.0 (Ar, Ar' : C _ιpso ) , 139.8 and 138.9 (Ar, Ar ^• : C _σ ) , 135.2 (BAF: C ₀ ) , 129.3 (q, J _C F = 31.4, BAF _: C _m ) , 129.3 and

128.5 (Ar, Ar' : C _p ) , 125.0 (q, J _C F = 272.4, BAF: CF ₃ ) , 124.3 and 123.7 (Ar, Ar ' : C _n ) , 117.9 (BAF: C _p ) , 29.2 and 28.9 ( CHMe ₂ , C'HMe ₂ ) , 24.5, 24.1, 23.0, and 22.5

(CHMeMe ' , C'HMeMe ') , 10.3 (PdMe) . Anal. Calcd for (C ₈₆ H ₉ oBClF ₂₄ N ₄ Pd ₂ ) : C, 54.52; H, 4.97; N, 2.96. Found: C, 54.97; H, 4.72; N, 2.71.

Example 9 Alternatively, the products of Examples 7 and 8 have been synthesized by stirring a 1:1 mixture of the appropriate PdMeCl compound and NaBAF in Et 0 for -1 h. Removal of solvent yields the dimer + 0.5 equiv of Na ⁺ (0Et ₂ ) BAF" . Washing the product mixture with hexane yields ether-free NaBAF, which is insoluble in CH ₂ C1 ₂ . Addition of CH ₂ C1 ₂ to the product mixture and filtration of the solution yields salt-free dimer: ¹ H NMR spectral data are identical with that reported above. For a synthesis of C0DPdMe ₂ , see: Rudler-

Chauvin, M. , and Rudler, H. J. Organomet. Chem. 1977, 134, 115-119.

Example 10 [ (2,6-i-PrPh) ₂ DABMe ₂ ]PdMe ₂ A Schlenk flask containing a mixture of [(2,6-i- PrPh) ₂ DABMe ₂ ] PdMeCl (2.00 g, 3.57 mmol) and 0.5 equiv of Me ₂ Mg (97.2 mg, 1.79 mmol) was cooled to -78 °C, and the reaction mixture was then suspended in 165 mL of Et ₂ 0. The reaction mixture was allowed to warm to room temperature and then stirred for 2 h, and the resulting brown solution was then filtered twice. Cooling the solution to -30 °C yielded brown single crystals (474.9 mg, 24.6%, 2 crops) : ^X H NMR (C ₆ D ₆ , 400 MHz) δ 7.2-7.1 (m, 6, H _ary ι) , 3.17 (septet, 4, J = 6.92, CHMe ₂ ) , 1.39 (d, 12, J = 6.74, CHMeMe') , 1.20 (N=C(Me) -C (Me) =N) ,

1.03 (d, 12, J = 6.89, CHMeMe') , 0.51 (s, 6, PdMe) ; ¹³ C NMR (C ₆ D ₆ , 100 MHz) δ 168.4 (N=C-C=N) , 143.4 (Ar: Cipso) , 138.0 (Ar: C _σ ) , 126.5 (Ar : C _p ) , 123.6 (Ar: C _m ) , 28.8 (CHMe ₂ ) , 23.6 and 23.5 (CHMeMe') , 19.5 (N=C(Me) - C(Me)=N) , -4.9 (J _C H = 127.9, PdMe) . Anal. Calcd for (C ₃₀ H ₄₆ N ₂ Pd) : C, 66.59; H, 8.57; N, 5.18. Found: C, 66.77; H, 8.62; N, 4.91.

Example 11

[ (2,6-i-PrPh) ₂ DABH ₂ ] PdMe ₂ The synthesis of this compound in a manner analogous to Example 10, using 3.77 mmol of ArN=C(H)- C(H)=NAr and 1.93 mmol of Me ₂ Mg yielded 722.2 mg

(37.4%) of a deep brown microcrystalline powder upon recrystallization of the product from a hexane/toluene solvent mixture.

This compound was also synthesized by the following method: A mixture of Pd(acac) (2.66 g, 8.72 mmol) and corresponding diimine (3.35 g, 8.90 mmol) was suspended in 100 mL of Et ₂ 0, stirred for 0.5 h at room temperature, and then cooled to -78°C. A solution of Me ₂ Mg (0.499 g, 9.18 mmol) in 50 mL of Et ₂ 0 was then added via cannula to the cold reaction mixture. After stirring for 10 min at -78 ^Q C, the yellow suspension was allowed to warm to room temperature and stirred for an additional hour. A second equivalent of the diimine was then added to the reaction mixture and stirring was continued for -4 days. The brown Et ₂ 0 solution was then filtered and the solvent was removed in vacuo to yield a yellow-brown foam. The product was then extracted with 75 mL of hexane, and the resulting solution was filtered twice, concentrated, and cooled to -30°C overnight to yield 1.43 g (32.0%) of brown powder: H NMR (C ₆ D ₆ , 400 MHz) δ 7.40 (s, 2, N-C(H)- C(H)=N), 7.12 (s, 6, H _ary i) , 3.39 (septet, 4, J = 6.86, CHMe ₂ ) , 1.30 (d, 12, J ■ 6.81, CHMeMe'), 1.07 (d, 12, J = 6.91, CHMeMe'), 0.77 (s, 6, PdMe); ¹³ C NMR (C6D ₆ , 100 MHz) δ 159.9 (J _CH = 174.5, N-C(H) -C(H) =N) , 145.7 (Ar: Ci _pso ), 138.9 (Ar: C ₀ ) , 127.2 (Ar: C _p ) , 123.4 (Ar: C _m ) , 28.5 (CHMe ₂ ), 24.4 and 22.8 (CHMeMe'), -5.1 (J _CH = 128.3, PdMe). Anal. Calcd for (C ₂₈ H ₄₂ N ₂ Pd) : C, 65.55, H, 8.25; N, 5.46. Found: C, 65.14; H, 8.12; N, 5.14.

Example 12 [ (2,6-MePh) ₂ DABH ₂ ] PdMe ₂ This compound was synthesized in a manner similar to the second procedure of Example 11 (stirred for 5 h at rt) using 5.13 mmol of the corresponding diimine and 2.57 mmol of Me ₂ Mg. After the reaction mixture was filtered, removal of Et ₂ 0 in vacuo yielded 1.29 g (62.2%) of a deep brown microcrystalline solid: ¹ H NMR (C ₆ D ₆ , 100 MHz, 12°C) δ 6.98 (s, 2, N=C(H) -C (H) =N) , 6.95 (s, 6, H _ary ι) , 2.13 (s, 12, Ar: Me), 0.77 (s, 6, PdMe); ¹³ C NMR (C ₆ D ₆ , 400 MHz, 12°C) δ 160.8 (J _CH = 174.6, N=C(H) -C(H)=N) , 147.8 (Ar: C _ipso ) , 128.2 (Ar: C _π ,) , 128.15 (Ar: C _σ ) , 126.3 (Ar: C _p ) , 18.2 (Ar: Me), - 5.5 (J _CH = 127.6, Pd-Me) . Example 13

[ (2,6-i-PrPh) ₂ DABH ₂ ]NiMe ₂ The synthesis of this compound has been reported (Svoboda, M.; torn Dieck, H. J. Organomet . Chem. 1980, 191 , 321-328) and was modified as follows: A mixture of Ni(acac) ₂ (1.89 g, 7.35 mmol) and the corresponding diimine (2.83 g, 7.51 mmol) was suspended in 75 mL of Et ₂ 0 and the suspension was stirred for 1 h at room temperature. After cooling the reaction mixture to - 78°C, a solution of Me ₂ Mg (401 mg, 7.37 mmol) in 25 mL of Et ₂ 0 was added via cannula. The reaction mixture was stirred for 1 h at -78°C and then for 2 h at 0°C to give a blue-green solution. After the solution was filtered, the Et ₂ 0 was removed in vacuo to give a blue- green brittle foam. The product was then dissolved in hexane and the resulting solution was filtered twice, concentrated, and then cooled to -30°C to give 1.23 g (35.9% , one crop) of small turquoise crystals.

Example 14 [ (2,6-i-PrPh) ₂ DABMe ₂ ]NiMe ₂ The synthesis of this compound has been reported (Svoboda, M.; torn Dieck, H. J. Organomet . Chem. 1980, 191 , 321-328) and was synthesized according to the above modified procedure (Example 13) using Ni(acac) ₂

(3.02 g, 11.75 mmol) , the corresponding diiWrrϊe'"T4.80 g, 11.85 mmol) and Me ₂ Mg (640 mg, 11.77 mmol) . A turquoise powder was isolated (620 mg, 10.7%) .

Example 15 { [ (2,6-MePh) ₂ DABMe ₂ ] PdMe(MeCN) }BAF ^"

To a mixture of [ (2, 6-MePh) ₂ DABMe ₂ ] PdMeCl (109.5 mg, 0.244 mmol) and NaBAF (216.0 mg, 0.244 mmol) were added 20 mL each of Et ₂ 0 and CH ₂ C1 ₂ and 1 mL of CH ₃ CN. The reaction mixture was then stirred for 1.5 h and then the NaCI was removed via filtration. Removal of the solvent in vacuo yielded a yellow powder, which was washed with 50 mL of hexane. The product (269.6 mg, 83.8%) was then dried in vacuo: ¹ H NMR (CD ₂ C1 , 400 MHz) δ 7.73 (s, 8, BAF: H _σ ) , 7.57 (s, 4, BAF: H _p ) , 7.22-7.16 (m, 6, H _aryl ) , 2.23 (s, 6, Ar: Me) , 2.17 (s, 6, Ar' : Me) , 2.16, 2.14, and 1.79 (s, 3 each, N=C(Me)- C' (Me)=N, NCMe) , 0.38 (s, 3, PdMe) ; ¹³ C NMR (CD ₂ C1 ₂ , 100 MHz) δ 180.1 and 172.2 (N=C-C'=N) , 162.1 (q, J _B c = 49.9, BAF: C _ipso ) , 142.9 (Ar, Ar' : C _D ) , 135.2 (BAF: C _D ) , 129.3 (Ar: C _m ) , 129.2 (q, J _CF = 30.6, BAF: C _m ) , 129.0 (Ar' : Cm) , 128.4 (Ar: C _p ) , 128.2 (Ar: C _c ) , 127.7 (Ar' : C _p ) , 127.4 (Ar ¹ : C ₀ ) , 125.0 (q, J _CF = 272.4, BAF: CF ₃ ) , 121.8 (NCMe), 117.9 (BAF: C _p ) , 20.2 and 19.2 (N=C(Me)- C' (Me)=N) , 18.0 (Ar: Me) , 17.9 (Ar' : Me) , 5.1 and 2.3 (NCMe, PdMe) . Anal. Calcd for (C ₅₅ H ₄₂ BF ₂₄ N ₃ Pd) : C,

50.12; H, 3.21; N, 3.19. Found: C, 50.13; H, 3.13, N, 2.99.

Example 16 ! [ (4-MePh) ₂ DABMe ₂ ] PdMe (MeCN) }BAF ^" Following the procedure of Example 15, a yellow powder was isolated in 85% yield: ¹ H NMR (CD ₂ C1 ₂ , 400 MHz) δ 7.81 (S, 8, BAF: H ₀ ) , 7.73 (s, 4, BAF: H _p ) , 7.30 (d, 4, J = 8.41, Ar, Ar ' : E _w ) , 6.89 (d, 2, J = 8.26, Ar: H _σ ) , 6.77 (d, 2, J = 8.19, Ar ' : H ₀ ) , 2.39 (s, 6, Ar, Ar' : Me) , 2.24, 2.17 and 1.93 (s, 3 each, N=C(Me)- C' (Me)=N, NCMe)Pd-Me; ¹³ C NMR (CD ₂ Cl ₂ , 100 MHz) δ 180.7 and 171.6 (N=C-C'=N) , 162.1 (q, J _B c = 49.8, BAF: C _ιpao ) , 143.4 and 142.9 (Ar, Ar ' : C _ιpso ) , 138.6 and 138.5 (Ar,

r' : Cp) , 135.2 (BAF: C ₀ ) , 130.6 and 130.4 (Ar, Ar' : C _m ) , 129.3 (q, JCF = 31.6, BAF: C _m ) , 125.0 (q, J _CF = 272.5, BAF: CF ₃ ) , 122.1 (NCMe) , 121.0 and 120.9 (Ar, Ar' : C _c ) , 117.9 (BAF: C _p ) , 21.5 (ArN=C(Me)) , 21.1 (Ar, Ar' : Me) , 19.7 (ArN=C' (Me) ) , 6.2 and 3.0 (NCMe, PdMe) . Anal. Calcd for (C ₅₃ H ₃₈ BF ₂₄ N ₃ Pd) : C, 49.34; H, 2.97: N, 3.26. Found: C, 49.55; H, 2.93; N, 3.10.

Example 17 [ (2,6-MePh) ₂ DABMe ₂ ] PdMe (Et ₂ 0.) BAF ^" A Schlenk flask containing a mixture of [(2,6-i- PrPh) ₂ DABMe ₂ ] PdMe ₂ (501 mg, 0.926 mmol) and H ⁺ (OEt ₂ ) ₂ BAF ^" (938 mg, 0.926 mmol) was cooled to -78°C. Following the addition of 50 mL of Et ₂ 0, the solution was allowed to warm and stirred briefly (-15 min) at room temperature. The solution was then filtered and the solvent was removed in vacuo to give a pale orange powder (1.28 g, 94.5%) , which was stored at -30°C under an inert atmosphere: ^-H NMR (CD ₂ C1 ₂ , 400 MHz, -60°C) δ 7.71 (s, 8, BAF: H ₀ ) , 7.58 (s, 4, BAF: H _p ) , 7.4 - 7.0 (m, 6, H _ary ι) , 3.18 (q, 4, J = 7.10, O (CJY ₂ CH ₃ ) ₂ ) , 2.86 (septet, 2, J = 6.65, CHMe ₂ ) , 2.80 (septet, 2, J = 6.55, C'flMe ₂ ) , 2.18 and 2.15 (N=C (Me) -C (Me) =N) , 1.34, 1.29, 1.14 and 1.13 (d, 6 each, J = 6.4-6.7, CHMeMe', C'HMeMe') , 1.06 (t, J = 6.9, O (CH ₂ CH ₃ ) ) , 0.33 (s, 3, PdMe) ; ¹³ C NMR (CD ₂ Cl ₂ , 100 MHz, -60°C) δ 179.0 and 172.1 (N=C-C'=N) , 161.4 (q, J _BC = 49.7, BAF: C _ipso ) , 140.21 and 140.15 (Ar, Ar ' : C _ipso ) , 137.7 and 137.4 (Ar, Ar' : C _σ ) , 134.4 (BAF: C _p ) , 128.3 (q, J _C F = 31.3, BAF: C _m ) , 128.5 and 128.2 (Ar, Ar ' : C _p ) , 124.2 (q, J _CF = 272.4, BAF: CF ₃ ) , 117.3 (BAF: C _p ) , 71.5 (0 ( H ₂ CH ₃ ) ₂ ) , 28.7 (CHMe ₂ ) , 28.4 (C'HMe ₂ ) , 23.7, 23.6, 23.1 and 22.6 (CHMeMe', C'HMeMe') , 21.5 and 20.7 (N=C (Me) -C (Me) =N) , 14.2 (0(CH ₂ CH ₃ ) ₂ ) ₂ , 8.6 (PdMe) . Anal. Calcd for (C ₆₅ H ₆₅ BF ₂₄ N ₂ OPd) : C, 53.35; H, 4.48; N, 1.91. Found: C, 53.01; H, 4.35; N, 1.68.

Example 18 [ (2,6-MePh) ₂ DABH ₂ ]PdMe(Et ₂ 0)BAF ^" Following the procedure of Example 17, an orange powder was synthesized in 94.3% yield and stored at - 30°C: ^X H NMR (CD ₂ Cl , 400 MHz, -60°C) δ 8.23 and 8.20 (s, 1 each, N=C (H) -C (H) =N) , 7.72 (s, 8, BAF: H _σ ) , 7.54 (S, 4, BAF: Hp) , 7.40 - 7.27 (m, 6, H _ar yl> / 3.32 (q, 4, J = 6.90, 0(CH2CH ₃ ) ₂ ) , 3.04 and 3.01 (septets, 2 each, J = 6.9 - 7.1, CHMe ₂ and C*ϋMe ₂ ) , 1.32, 1.318, 1.14 and 1.10 (d, 6 each, J = 6.5 - 6.8, CHMeMe' and C'HMeMe') , 1.21 (t, 6, J = 6.93, 0(CH CH ₃ ) ₂ ) , 0.70 (s, 3, PdMe) ; ¹³ C NMR (CD ₂ C1 ₂ , 100 MHz, -60°C) δ 166.9 (J _C H = 182.6, N=C(H)) , 161.5 (J _BC = 49.7, BAF: C _ipso ) , 161.3 (J _CH = 181.6, N=C' (H)) , 143.0 and 141.8 (Ar, Ar ' : Ci _pso ) , 138.7 and 137.8 (Ar, Ar ' : C _σ ) , 134.4 (BAF: C _σ ) , 129.1 and 128.8 (Ar, Ar' : C _p ) , 128.3 (J _CF = 31.3, BAF: C _m ) , 124.0 and 123.9 (Ar, Ar ¹ : C _m ) , 117.3 (BAF: C _p ) , 72.0 (0(CH ₂ CH ₃ ) ₂ ) , 28.5 and 28.4 (CHMe ₂ , C'HMe ₂ ) , 25.2, 24.1, 21.9 and 21.7 (CHMeMe', C'HMeMe'), 15.2 (O (CH ₂ CH ₃ ) ₂ ) , 11.4 (J _CH = 137.8, PdMe) . Anal. Calcd for

(C ₆₃ H ₆₁ BF ₂₄ N ₂ 0Pd) : C, 52.72; H, 4.28; N, 1.95. Found: C, 52.72; H, 4.26; N, 1.86.

Example 19 [ (2,6-MePh) ₂ DABMe ₂ ]NiMe(Et ₂ 0)BAF ^" Following the procedure of Example 17, a magenta powder was isolated and stored at -30°C: ¹ H NMR (CD ₂ C1 ₂ , 400 MHz, -60°C; A H ₂ 0 adduct and free Et ₂ 0 were observed.) δ 7.73 (s, 8, BAF: H ₀ ) , 7.55 (s, 4, BAF: H _p ) , 7.4 - 7.2 (m, 6, H _ary l) , 3.42 (s, 2, 0H ₂ ) , 3.22 (q, 4, 0(CH ₂ CH ₃ ) ₂ ) , 3.14 and 3.11 (septets, 2 each, J = 7.1, CflMe ₂ , C'HMe ₂ ) , 1.95 and 1.78 (s, 3 each, N=C(Me) -C (Me) =N) , 1.42, 1.39, 1.18 and 1.11 (d, 6 each, J = 6.6 - 6.9, CHMeMe' and C'HMeMe') , 0.93 (t, J = 7.5, 0(CH ₂ CH ₃ ) ₂ ) , -0.26 (s ,3, NiMe) ; ¹³ C NMR (CD ₂ C1 100 MHz, -58°C) δ 175.2 and 170.7 (N=C-C'=N) , 161.6 (q, J _BC = 49.7, BAF: Ci _pso ) , 141.2 (Ar: C _ipso ) , 139.16 and 138.68 (Ar, Ar ' : C ₀ ) , 136.8 (Ar ' : C _ιpso ) , 134.5 (BAF: C _c ) , 129.1 and 128.4 (Ar, Ar ' : C _p ) , 128.5

(q, J _CF = 32.4, BAF: C _m ) , 125.0 and 124.2 (Ar, Ar ' : Cm) , 124.3 (q, J _C F = 272.5, BAF: CF ₃ ) , 117.4 (BAF: C _p ) , 66.0 (0(CH CH ₃ ) ₂ ) , 29.1 (CHMe ₂ ) , 28.9 (C'HMe ₂ ) , 23.51, 23.45, 23.03, and 22.95 (CHMeMe', C'HMeMe') , 21.0 and 19.2 (N=C(Me) -C (Me) =N) , 14.2 (OCH ₂ CH ₃ ) ₂ ) , -0.86 (J _C H = 131.8, NiMe) . Anal. Calcd for (C ₆₅ H ₆₅ BF ₂₄ N ₂ NiO) : C, 55.15; H, 4.63; N, 1.98. Found: C, 54.74; H, 4.53; N, 2.05.

Example 2Q ^' [-(2,6-MePh) ₂ DABH ₂ ]NiMe(Et ₂ 0)BAF ^"

Following the procedure of Example 17, a purple powder was obtained and stored at -30°C: ¹ H NMR (CD ₂ C1 ₂ , 400 MHz, -80°C; H ₂ 0 and Et 0 adducts were observed in an 80:20 ratio, respectively.) δ 8.31 and 8.13 (s, 0.8 each, N=C (H) - ' (H) =N; H ₂ 0 Adduct) , 8.18 and 8.00 (s, 0.2 each, N=C (H) -C (H) =N; Et 0 Adduct) , 7.71 (s, 8 BAF: C _c ) , 7.53 (s, 4, BAF: C _p ) , 7.5 - 7.0 (m, 6, H _aryi ) , 4.21 (s, 1.6, 0H ₂ ) , 3.5 - 3.1 (m, 8, 0(CH ₂ CH ₃ ) ₂ , CHMe ₂ , C'HMe ₂ ), 1.38, 1.37, 1.16 and 1.08 (d, 4.8 each, CHMeMe', C'HMeMe',- H ₂ 0 Adduct; These peaks overlap with and obscure the CHMe doublets of the Et ₂ 0 adduct.) , 0.27 (s, 2.4, PdMe; H ₂ 0 Adduct) , 0.12 (s, 0.6, PdMe: Et 0 Adduct) .

Examples 21-23 The rate of exchange of free and bound ethylene was determined by H NMR line broadening experiments at -85°C for complex (XI) , see the Table below. The NMR instrument was a 400 MHz Varian® NMR spectrometer. Samples were prepared according to the following procedure: The palladium ether adducts { [(2,6-i- PrPh) ₂ DABMe ₂ ] PdMe (OEt ₂ ) }BAF, { [ (2 , 6-i- PrPh) ₂ An] PdMe (OEt ₂ ) }BAF, and { [{2,6-i-

PrPh) DABH ] PdMe (OEt ₂ ) }BAF were used as precursors to (XI) , and were weighed (-15 mg) in a tared 5 mm dia. NMR tube in a nitrogen-filled drybox. The tube was then capped with a septum and Parafilm® and cooled to -80°C. Dry, degassed CD ₂ C1 ₂ (700 μL) was then added to the palladium complex via gastight syringe, and the

be was shaken and warmed briefly to grve"a ^* homogeneous solution. After acquiring a -85°C NMR spectrum, ethylene was added to the solution via gastight syringe and a second NMR spectrum was acquired at -85°C. The molarity of the BAF counterion was calculated according to the moles of the ether adduct placed in the NMR tube. The molarity of (XI) and free ethylene were calculated using the BAF peaks as an internal standard. Line-widths (W) were measured at half-height in units of Hz for the complexed ethylene signal (usually at 5 to 4 ppm) and were corrected for line widths (W ₀ ) in the absence of exchange.

For (XI) the exchange rate was determined from the standard equation for the slow exchange approximation: k = (W - W ₀ )π/[=] , where [=] is the molar concentration of ethylene. These experiments were repeated twice and an average value is reported below.

Rate Constants for Ethylene Exchange ³

^a The Ti of free ethylene is 15 sec. A pulse delay of 60 sec and a 30° pulse width were used.

Example 24

Anhydrous FeCl ₂ (228 mg, 1.8 mmol) and (2,6-i- PrPh) ₂ DABAn (1.0 g, 2.0 mmol) were combined as solids and dissolved in 40 ml of CH ₂ C1 ₂ . The mixture was stirred at 25°C for 4 hr. The resulting green solution was removed from the unreacted FeCl ₂ via filter cannula. The solvent was removed under reduced

pressure resulting in a green solid (0.95 g, 84% yield) .

A portion of the green solid (40 mg) was immediately transferred to another Schlenk flask and dissolved in 50 ml of toluene under 1 atm of ethylene. The solution was cooled to 0°C, and 6 ml of a 10% MAO solution in toluene was added. The resulting purple solution was warmed to 25°C and stirred for 11 hr. The polymerization was quenched and the polymer precipitated by acetone. The resulting polymer was washed with 6M HC1, water and acetone. Subsequent drying of the polymer resulted in 60 mg of white polyethylene. ^X H NMR (CDC1 ₃ , 200 MHz) δl.25 (CH ₂ , CH) δ 0.85 ( , CH ₃ ) . Example 25

(2-t-BuPh) ₂ DABMe ₂ A Schlenk tube was charged with 2- t-butylaniline (5.00 mL, 32.1 mmol) and 2, 3-butanedione (1.35 mL, 15.4 mmol) . Methanol (10 mL) and formic acid (1 mL) were added and a yellow precipitate began to form almost immediately upon stirring. The reaction mixture was allowed to stir overnight. The resulting yellow solid was collected via filtration and dried under vacuum. The solid was dissolved in ether and dried over Na2Sθ4 for 2-3 h. The ether solution was filtered, condensed and placed into the freezer (-30°C) . Yellow crystals were isolated via filtration and dried under vacuum overnight (4.60 g, 85.7%) : *H NMR (CDCI3, 250 MHz) δ 7.41 (dd, 2H, J = 7.7, 1.5 Hz, H _m ) , 7.19 (td, 2H, J= 7.5, 1.5 Hz, H _m or H _p ) , .7.07 (td, 2H, J = 7.6, 1.6 Hz, H _m or H _p ) , 6.50 (dd, 2H, J = 7.7, 1.8 Hz, H ₀ ) , 2.19 (s, 6H, N=C(Me) -C(Me)=N) , 1.34 (s, 18H, C( H _. 3)3) .

Examples 26 and 7 General Polymerization Procedure for Examples 26 and 27: In the drybox, a glass insert was loaded with [ (η ³ -C ₃ H ₅ ) Pd(μ-Cl) ] ₂ (11 mg, 0.03 mmol) , NaBAF (53 mg, 0.06 mmol) , and an α-diimine ligand (0.06 mmol) . The insert was cooled to -35°C in the drybox freezer, 5 mL

jf C ₆ D ₆ 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 18 h. An aliquot of the solution was used to acquire a ² H NMR spectrum. The remaining portion was added to -20 mL of MeOH in order to precipitate the polymer. The polyethylene was isolated and dried under vacuum

Example 26 α-Diimine was (2, 6-i-PrPh) ₂ DABMe ₂ . Polyethylene (50 mg) was isolated as a solid. ^X H NMR spectrum (CςDs ) is consistent with the production of 1- and 2- butenes and branched polyethylene.

Example α-Diimine was (2, 6-i-.PrPh) DABAn. Polyethylene (17 mg) was isolated as a solid. ¹ H NMR spectrum ( ζDξ ) is consistent with the production of branched polyethylene.

Example 28 [(2,6-i-PrPh) ₂ DABH ₂ ]NiBr ₂

The corresponding diimine (980 mg, 2.61 mmol) was dissolved in 10 mL of CH ₂ C1 ₂ in a Schlenk tube under a N ₂ atmosphere. This solution was added via cannula to a suspension of (DME)NiBr ₂ (DME = 1,2-dimethoxyethane) (787 mg, 2.55 mmol) in CH ₂ C1 ₂ (20 mL) . The resulting red/brown mixture was stirred for 20 hours. The solvent was evaporated under reduced pressure resulting in a red/brown solid. The product was washed with 3 x 10 mL of hexane and dried in vacuo. The product was isolated as a red/brown powder (1.25 g, 82% yield) .

Example 2?

[ (2,6-i-PrPh) ₂ DABMe ₂ ]NiBr ₂ Using a procedure similar to that of Example 28, 500 mg (1.62 mmol) (DME)NiBr ₂ and 687 mg (1.70 mmol) of the corresponding diimine were combined. The product was isolated as an orange/brown powder (670 mg, 67% yield) .

Example 30 [ (2,6-MePh) ₂ DABH ₂ ]NiBr ₂ Using a procedure similar to that of Example 28, 500 mg (1.62 mmol) (DME)NiBr ₂ and 448 mg (1.70 mmol) of the corresponding diimine were combined. The product was isolated as a brown powder (622 mg, 80% yield) .

Example 31 [ (2,6-i-PrPh) ₂ DABAn]NiBr ₂ Using a procedure similar to that of Example 28, 500 mg (1.62 mmol) (DME)NiBr ₂ and 850 mg (1.70 mmol) of the corresponding diimine were combined. The product was isolated as a red powder (998 mg, 86% yield) . Anal. Calcd. for C ₃₆ H ₄ oN ₂ Br ₂ Ni : C, 60.12; H, 5.61; N, 3.89. Found C, 59.88; H, 5.20; N, 3.52. Example 32

[ (2,6-MePh) ₂ DABAn]NiBr ₂ The corresponding diimine (1.92 g, 4.95 mmol) and (DME)NiBr ₂ (1.5 g, 4.86 mmol) were combined as solids in a flame dried Schlenk under an argon atmosphere. To this mixture 30 mL of CH ₂ C1 ₂ was added giving an orange solution. The mixture was stirred for 18 hours resulting in a red/brown suspension. The CH ₂ C1 ₂ was removed via filter cannula leaving a red/brown solid. The product was washed with 2 x 10 mL of CH ₂ C1 ₂ and dried under vacuum. The product was obtained as a red/brown powder (2.5 g, 83% yield) .

Example 33 [ (2,6-MePh) ₂ DABMe ₂ ]NiBr ₂ Using a procedure similar to that of Example 32, the title compound was made from 1.5 g (4.86 mmol)

(DME)NiBr ₂ and 1.45 g (4.95 mmol) cf the corresponding diimine. The product was obtained as a brown powder (2.05 g, 81% yield) .

Example 34 [ (2, 6-i-PrPh) ₂ DABMe _: ] PdMeCl

(COD) PdMeCl (9.04 g, 34.1 mmol) was dissolved in 200 mi of methylene chloride. To this solution was added the corresponding diimine (13.79 g, 34.1 mmol) .

.The resulting solution rapidly changed color from yellow to orange-red. After stirring at room temperature for several hours it was concentrated to form a saturated solution of the desired product, and cooled to -40°C overnight. An orange solid crystallized from the solution, and was isolated by filtration, washed with petroleum ether, and dried to afford 12.54 g of the title compound as an orange powder. Second and third crops of crystals obtained from the mother liquor afforded an additional 3.22 g of product. Total yield = 87%.

Examples 35-39 The following compounds were made by a method similar to that used in Example 34.

Example Compound

35 [ (2,6-i-PrPh) ₂ DABH ₂ ] PdMeCl

36 [ (2,6-i-PrPh) ₂ DABAn] PdMeCl

37 [(Ph) ₂ DABMe ₂ ] PdMeCl 38 [(2,6-EtPh) ₂ DABMe ₂ ] PdMeCl

39 [ (2,4, 6-MePh) ₂ DABMe ₂ ] PdMeCl

Note : The diethyl ether complexes described in Examples 41-46 are unstable in non-coordinating solvents such as methylene chloride and chloroform. They are characterized by ^X H ΝMR spectra recorded in CD ₃ CΝ; under these conditions the acetonitrile adduct of the Pd methyl cation is formed. Typically, less than a whole equivalent of free diethylether is observed by *H NMR when [ (R) ₂ DAB (R' ) ₂ ] PdMe (OEt ₂ )X is dissolved in CD ₃ CN. Therefore, it is believed the complexes designated as " ( [ (R) ₂ DAB (R- ) ₂ ] PdMe (OEt ₂ ) }X" below are likely mixtures of { [ (R) ₂ DAB(R' ) ₂ ] PdMe (OEt ₂ ) }X and [ (R) ₂ DAB (R' ) ₂ ] PdMeX, and in the latter complexes the X ligand (SbF ₆ , BF ₄ , or

PFg) is weakly coordinated to palladium. A formula of the type " { [ (R) ₂ DAB (R' ) ₂ ] PdMe (OEt ₂ ) }X" is a "formal" way of conveying the approximate overall composition of

this compound, but may not accurately depict the exact coordination to the metal atom.

Listed below are the ¹³ c NMR data for Example 36.

¹³ C NMR data

{ [ (4-Me ₂ NPh) ₂ DABMe ₂ ] PdMe (MeCN) }SbF ₆ -MeCN

A procedure analogous to that used in Example 54, using (4-Me ₂ NPh) ₂ DABMe ₂ in place of (2-C ₆ H ₄ - Bu) ₂ DABMe ₂ , afforded { [ (4-NMe ₂ Ph) ₂ DABMe ₂ ] PdMe (MeCN) }SbF ₆ -MeCN as a purple solid (product was not recrystallized in this instance) . ^X H NMR (CD C1 ₂ ) δ 6.96 (d, 2H, H _ar y _l ) . 6.75 (mult, 6H, Hary _l )/ 3.01 (s, 6H, NMe ₂ ), 2.98 (s, 6H, NMe' ₂ ) , 2.30, 2.18, 2.03, 1.96 (s's, 3H each, N=CMe, N=CMe', and free and coordinated N≡CMe) , 0.49 (s, 3H, Pd-Me) . Example 1

{ [ (2,6-i-PrPh) ₂ DABMe ₂ ]PdMe(Et ₂ 0) _n }SbF ₆ ^" [ (2,6-i-PrPh) ₂ DABMe ₂ ] PdMeCl (0.84 g, 1.49 mmol) was suspended in 50 mL of diethylether and the mixture cooled to -40 ^C C. To this was added AgSbF ₆ (0.52 g, 1.50 mmol) . The reaction mixture was allowed to warm to room temperature, and stirred at room temperature for 90 min. The reaction mixture was then filtered, giving a pale yellow filtrate and a bright yellow precipitate. The yellow precipitate was extracted with 4 x 20 mL 50/50 methylene chloride/diethyl ether. The filtrate and extracts were then combined with an additional 30 mL diethyl ether. The resulting solution was then concentrated to half its original volume and 100 mL of petroleum ether added. The resulting precipitate was filtered off and dried, affording 1.04 g of the title compound as a yellow-orange powder (83% yield) . ^H NMR (CD ₃ CN) δ 7.30 (mult, 6H, H _ary ι) , 3.37 [q, free 0(CH ₂ CH ₃ ) ₂ ], 3.05-2.90 (overlapping sept's, 4H, CHMe ₂ ) , 2.20 (s, 3H, N=CMe) , 2.19 (s, 3H, N=CMe ' ) , 1.35-1.14 (overlapping d's, 24H, CHMe ₂ ) , 1.08 (t, free 0(CH ₂ Ctf ₃ ) ₂ ] , 0.28 (s, 3H, Pd-Me) . This material contained 0.4 equiv of Et ₂ 0 per Pd, as determined by ^-H NMR integration.

Example 2 { [ (2,6-i-PrPh) ₂ DABMe ₂ ]PdMe(Et ₂ 0) _n }BF ₄ ^"

A procedure analogous to that used in Example 41, using AgBF ₄ in place of AgSbF ₆ , afforded the title compound as a mustard yellow powder in 61% yield. This

■. material contained 0.3 equiv of Et ₂ 0 per Pd, as determined by *H NMR integration. ¹ H NMR in CD ₃ CN was otherwise identical to that of the compound made in Example 41.

Example 43

{ [ (2,6-i-PrPh) ₂ DABMe ₂ ] PdMe (Et ₂ 0) _n }PF ₆ ^" A procedure analogous to that used in Example 41, using AgPF ₆ in place of AgSbFβ, afforded the title compound as a yellow-orange powder in 72% yield. This material contained 0.4 equiv of Et ₂ 0 per Pd, as determined by K NMR integration. ¹ H NMR in CD ₃ CN was identical to that of the compound of Example 41.

Example 44 { [ (2, 6-i-PrPh) ₂ DABH ₂ ] PdMe (Et ₂ 0) _n }SbF ₆ ^"

A procedure analogous to that used in Example 41, using [ (2, 6-i-PrPh) ₂ DABH ₂ ] PdMeCl in place of [(2,6-i- PrPh) ₂ DABMe ₂ ] PdMeCl, afforded the title compound in 71% yield. ³ -H NMR (CD ₃ CN) δ 8.30 (s, 2H, N=CH and N=CH') , 7.30 (s, 6H, H _ary ι) , 3.37 [q, free 0(CH ₂ CH ₃ ) ₂ ] , 3.15

(br, 4H, CHMe ₂ ) , 1.40-1.10 (br, 24H, CHMe ₂ ) , 1.08 (t, free 0(CH CH ₃ ) ₂ ] , 0.55 (s, 3H, Pd-Me) . This material contained 0.5 equiv of Et ₂ 0 per Pd, as determined by ¹ H NMR integration. Example 45

{ [ (2,4,6-MePh) ₂ DABMe ₂ ]PdMe(Et ₂ 0) _π }SbF ₆ ^" {(2,4,6-MePh) ₂ DABMe ₂ ] PdMeCl (0.50 g, 1.05 mmol) was partially dissolved in 40 mL 50/50 methylene chloride/diethylether. To this mixture at room temperature was added AgSbFβ (0.36 g, 1.05 mmol) . The resulting reaction mixture was stirred at room temperature for 45 min. It was then filtered, and the filtrate concentrated in vacuo to afford an oily solid. The latter was washed with diethyl ether and dried to afford the title compound as a beige powder. ^X H NMR (CD ₃ CN) δ 6.99 (s, 4H, H _aryi ) , 3.38 [q, free 0(CH ₂ CH ₃ ) ₂ ] , 2.30-2.00 (overlapping s's, 24H, N=CMe, N=CMe' and aryl Me's) , 1.08 (t, free 0(CH ₂ CH ₃ ) ₂ ] , 0.15

_. s , 3H, Pd-Me) . This material contained- 0'.7 equiv of Et ₂ 0 per Pd, as determined by ^λ H MR integration.

Example 46

{ [ (2,6-i-PrPh) ₂ DABAn]PdMe(Et ₂ 0) _n }SbF ₆ ^" A procedure analogous to that used in Example 41, using [ (2, 6-i-PrPh) ₂ DABAn] PdMeCl in place of [(2,6-i- PrPh) ₂ DABMe ₂ ] PdMeCl, afforded the title compound in 92% yield. ¹ H NMR (CD ₃ CN) δ 8.22 (br t, 2H, H _aryl ) , 7.60- 7.42 (br mult, 8H, H _ary ι) , 6.93 (br d, IH, H _ary ι) , 6.53 (br d, IH, H _ary ι) , 3.38 [q, free 0(CH ₂ CH ₃ ) ₂ ] , 3.30 (br mult, 4H, CflMe ₂ ) , 1.36 (br d, 6H, CHMe ₂ ) , 1.32 (br d, 6H, CHMe ₂ ), 1.08 (t, free 0{CH ₂ CH ₃ ) ₂ ] , 1.02 (br d, 6H, CHMe ₂ ) , 0.92 (br d, 6H, CHMe ₂ ) , 0.68 (s, 3H, Pd-Me) . The amount of ether contained in the product could not be determined precisely by ^H NMR integration, due to overlapping resonances.

Example 47 [ (2,6-i-PrPh) ₂ DABMe ₂ ]PdMe(OS0 ₂ CF ₃ ) A procedure analogous to that used in Example 41, using AgOS0 ₂ CF ₃ in place of AgSbFβ, afforded the title compound as a yellow-orange powder. ^X H NMR in CD ₃ CN was identical to that of the title compound of Example 41, but without free ether resonances.

Example 48 { [ (2,6-i-PrPh) ₂ DABMe ₂ ]PdMe(MeCN) }SbF ₆ ^"

[ (2,6-i-PrPh) ₂ DABMe ₂ ] PdMeCl (0.40 g, 0.71 mmol) was dissolved in 15 mL acetonitrile to give an orange solution. To this was added AgSbFβ (0.25 g, 0.71 mmol) at room temperature. AgCl immediately precipitated from the resulting bright yellow reaction mixture. The mixture was stirred at room temperature for 3 h. It was then filtered and the AgCl precipitate extracted with 5 mL of acetonitrile. The combined filtrate and extract were concentrated to dryness affording a yellow solid. This was recrystallized from methylene chloride/petroleum ether affording 0.43 g of the title compound as a bright yellow powder (Yield = 75%) . ^-H NMR (CDC1 ₃ ) δ 7.35-7.24 (mult, 6H, H _ary ι) , 2.91 (mult,

4H, CHMe ₂ ) , 2.29 (s, 3H, ") , 1.81 (s, 3H, N≡CMe) , 1.37-1.19 (overlapping d's, 24H, CHMe's) , 0.40 (s, 3H, Pd-Me) . This compound can also be prepared by addition of acetonitrile to { [(2,6-i- PrPh) ₂ DABMe ₂ ] PdMe (Et ₂ 0) }SbF ₆ ^" .

Example 49 { [ (Ph) ₂ DABMe ₂ ] PdMe (MeCN) }SbF ₆ ^" A procedure analogous to that used in Example 48, using [ (Ph) ₂ DABMe ₂ ] PdMeCl in place of [(2,6-i- PrPh) ₂ DABMe ₂ ] PdMeCl, afforded the title compound as a yellow microcrystalline solid upon recrystallization from methylene chloride / petroleum ether. This complex crystallizes as the acetonitrile solvate from acetonitrile solution at -40°C. ¹ H NMR of material recrystallized from methylene chloride/petroleum ether: (CDC1 ₃ ) δ 7.46 (mult, 4H, H _ary ι) , 7.30 (t, 2H, H _ary i) , 7.12 (d, 2H, Hary _l ) r 7.00 (d, 2H, H _aryi ) , 2.31 (s, 3H, N=CMe) , 2.25 (s, 3H, N=CMe ' ) , 1.93 (s, 3H, N≡CMe) , 0.43 (s, 3H, Pd-Me) . Example 50

{ [ (2,6-EtPh) ₂ DABMe ₂ ] PdMe (MeCN) }BAF ^" [ (2, 6-EtPh) ₂ DABMe ₂ ] PdMeCl (0.200 g, 0.396 mmol) was dissolved in 10 mL of acetonitrile to give an orange solution. To this was added NaBAF (0.350 g, 0.396 mmol) . The reaction mixture turned bright yellow and NaCI precipitated. The reaction mixture was stirred at room temperature for 30 min and then filtered through a Celite ^® pad. The Celite pad was extracted with 5 mL of acetonitrile. The combined filtrate and extract was concentrated in vacuo to afford an orange solid, recrystallization of which from methylene chloride / petroleum ether at -40°C afforded 0.403 g of the title compound as orange crystals (Yield = 74%) . ⁱ H NMR (CDCI ₃ ) δ 7.68 (s, 8H, H _ortho of anion) , 7.51 (s, 4H, H _para of anion) , 7.33-7.19 (mult, 6H, H _aryi of cation) , 2.56-2.33 (mult, 8H, CH ₂ CH ₃ ) , 2.11 (s, 3H, N=CMe) , 2.09 (s, 3H, N=CMe ' ) , 1.71 (s, 3H, N≡CMe) , 1.27-1.22 (mult, 12H, CH ₂ CH ₃ ) , 0.41 (s, 3H, Pd-Me) .

Example 51 { [(2,6-EtPh) ₂ DABMe ₂ ]PdMe(MeCN) }SbF ₆ ^" A procedure analogous to that used in Example 50, using AgSbFβ in place of NaBAF, afforded the title compound as yellow crystals in 99% yield after recrystallization from methylene chloride/petroleum ether at -40°C.

Example 52

[ (COD) PdMe (NCMe) ] SbF ₆ ^" To (COD) PdMeCl (1.25 g, 4.70 mmol) was added a solution of acetonitrile (1.93 g, 47.0 mmol) in 20 mL methylene chloride. To this clear solution was added AgSbFg (1.62 g, 4.70 mmol) . A white solid immediately precipitated. The reaction mixture was stirred at room temperature for 45 min, and then filtered. The yellow filtrate was concentrated to dryness, affording a yellow solid. This was washed with ether and dried, affording 2.27 g of [ (COD) PdMe (NCMe) ] SbF ₆ ^" as a light yellow powder (yield = 95%) . ^X H NMR (CD ₂ C1 ₂ ) δ 5.84 (mult, 2H, CH=CH) , 5.42 (mult, 2H, CH'=CH'), 2.65

(mult, 4H, CJffl'), 2.51 (mult, 4H, CHtf' ) , 2.37 (s, 3H, NCMe) , 1.18 (s, 3H, Pd-Me) .

Example 53 [ (COD) PdMe (NCMe) ]BAF ^" A procedure analogous to that used in Example 52, using NaBAF in place of AgSbFβ, afforded the title compound as a light beige powder in 96% yield.

Example 54 ( [ (2-t-BuPh) ₂ DABMe ₂ ] PdMe (MeCN) }SbF ₆ ^" To a suspension of (2-t-BuPh) ₂ DABMe ₂ (0.138 g, 0.395 mmol) in 10 mL of acetonitrile was added [ (COD) PdMe (NCMe) ] SbF ₆ (0.200 g, 0.395 mmol) . The resulting yellow solution was stirred at room temperature for 5 min. It was then extracted with 3 x 10 mL of petroleum ether. The yellow acetonitrile phase was concentrated to dryness, affording a bright yellow powder. Recrystallization from methylene chloride/petroleum ether at -40 °C afforded 180 mg of the title product as a bright yellow powder (yield = 61%) . ^X H NMR (CD ₂ C1 ₂ ) δ 7.57 (dd, 2H, H _aryi ) , 7.32 (mult, 4H, Haryl) _* 6.88 (dd, 2H, H _aryl ) , 6.78 (dd, 2H, Haryl) , 2.28 (s, 3H, N=CMe>, 2.22 (s, 3H, N=CMe ' ) , 1.78 (s, 3H, N≡CMe) , 1.48 (s, 18H, ^fc Bu) , 0.52 (s, 3H, Pd¬ Me) .

Example 55 { [ (Np) ₂ DABMe ₂ ] PdMe (MeCN) }SbF ₆ ^" A procedure analogous to that used in Example 54 , using (Np) ₂ DABMe ₂ in place of (2-t-BuPh) ₂ DABMe ₂ , afforded the title compound as an orange powder in 52% yield after two recrystallizations from methylene chloride/petroleum ether. ^X H NMR (CD C1 ₂ ) δ 8.20-7.19 (mult, 14 H, H _aromat i _c ) , 2.36 (d, J = 4.3 Hz, 3H,

N=CMe) , 2.22 (d, J = 1.4 Hz, 3H, N=CMe' ) , 1.32 (s, 3H, NCMe) , 0.22 (s, 3H, Pd-Me) .

Example 56 { [ (Ph ₂ CH) ₂ DABH ₂ ] PdMe (MeCN) }SbF ₆ ^" A procedure analogous to that used in Example 54 , using (Ph ₂ CH) ₂ DABH ₂ in place of (2-t-BuPh) ₂ DABMe ₂ , afforded the title compound as a yellow microcrystailine solid. ^X H NMR (CDC1 ₃ ) δ 7.69 (s, IH, N=CH) , 7.65 (s, IH, N=CH') , 7.44-7.08 (mult, 20H, H _aryi ) , 6.35 (2, 2H, CHPh ₂ ) , 1.89 (s, 3H, NCMe) , 0.78 (s, 3H, Pd-Me) .

Example 57 { [(2-PhPh) ₂ DABMe ₂ ] PdMe (MeCN) }SbF ₆ ^" A procedure analogous to that used in Example 54, using (2-PhPh) ₂ DABMe in place of (2-t-BuPh) ₂ DABMe ₂ , afforded the title compound as a yellow-orange powder in 90% yield. Two isomers, due to cis or trans orientations of the two ortho phenyl groups on either side of the square plane, were observed by ^X H NMR. ^X H NMR (CD ₂ C1 ₂ ) δ 7.80-6.82 (mult, 18H, H _ary ι), 1.98, 1.96, 1.90, 1.83, 1.77, 1.73 (singlets, 9H, N=CMe, N=CMe ' , NCMe for cis and trans isomers), 0.63, 0.61 (singlets, 3H, Pd-Me for cis and trans isomers) .

Example 58

{ [ (Ph) ₂ DAB(cyclo-CMe ₂ CH ₂ CMe ₂ -) ] PdMe (MeCN) }BAF ^" To a solution of [ (COD) PdMe (NCMe) ]BAF ^" (0.305 g, 0.269 mmol) dissolved in 15 mL of acetonitrile was added N,N' -diphenyl-2, 2' ,4,4 ' -tetramethyl- cyclopentyldiazine (0.082 g, 0.269 mmol) . A gold colored solution formed rapidly and was stirred at room temperature for 20 min. The solution was then extracted with 4 x 5 mL petroleum ether, and the acetonitrile phase concentrated to dryness to afford a yellow powder. This was recrystallized from methylene chloride/petroleum ether at -40°C to afford 0.323 g (90%) of the title compound as a yeHow-orange, crystalline solid. ^X H NMR (CDC1 ₃ ) δ 7.71 (s, 8H, H _orth o of anion) , 7.54 (s, 4H, H _para of anion) , 7.45-6.95 (mult, 10H, H _ary ι of cation) , 1.99 (s, 2H, CH ₂ ), 1.73 (s, 3H, NCMe), 1.15 (s, 6H, Me ₂ ) , 1.09 (s, 6H, Me' ₂ ) , 0.48 (s, 3H, Pd-Me) .

Example 9 { [(2,6-i-PrPh) ₂ DABMe ₂ ]Pd(CH ₂ CH ₂ CH ₂ C0 ₂ Me) }SbF _€ ^" Under a nitrogen atmosphere { [(2,6-i- PrPh) ₂ DABMe ₂ ] PdMe (Et ₂ 0) }SbF ₆ ^" (3.60 g, 4.30 mmol) was weighed into a round bottom flask containing a magnetic stirbar. To this was added a -40°C solution of methyl acrylate (1.85 g, 21.5 mmol) dissolved in 100 ml of methylene chloride. The resulting orange solution was

stirred for 10 min, while being allowed to warm to room temperature. The reaction mixture was then concentrated to dryness, affording a yellow-brown solid. The crude product was extracted with methylene chloride, and the orange-red extract concentrated, layered with an equal volume of petroleum ether, and cooled to -40°C. This afforded 1.92 g of the title compound as yellow-orange crystals. An additional 1.39 g was obtained as a second crop from the mother liquor; total yield = 91%. -H NMR (CD ₂ C1 ₂ ) δ 7.39-7.27 (mult, 6H, Haryl) . 3.02 (s, 3H, OMe) , 2.97 (sept, 4H, CHMe ₂ ) , 2.40 (mult, 2H, CH ) , 2.24 (s, 3H, N=CMe) , 2.22 (s, 3H, N=CMe') , 1.40-1.20 (mult, 26H, CHMe ₂ and CH ₂ ' ) , 0.64 (mult, 2H, CH ₂ ' ' ) . Exampl 60

( [ (2,6-i-PrPh) ₂ DABH ₂ ] Pd (CH ₂ CH ₂ CH ₂ C0 ₂ Me) }SbF ₆ ^" AgSbF ₆ (0.168 g, 0.489 mmol) was added to a -40°C solution of ( [ (2,6-i-PrPh) ₂ DABH ₂ ] PdMeCl (0.260 g, 0.487 mmol) and methyl acrylate (0.210 g, 2.44 mmol) in 10 mL methylene chloride. The reaction mixture was stirred for 1 h while warming to room temperature, and then filtered. The filtrate was concentrated in vacuo to give a saturated solution of the title compound, which was then layered with an equal volume of petroleum ether and cooled to -40°C. Red-orange crystals precipitated from the solution. These were separated by filtration and dried, affording 0.271 g of the title compound (68% yield) . ^X H NMR (CD ₂ C1 ₂ ) δ 8.38 (s, IH, N=CH) , 8.31 (s, IH, N=CH'), 7.41-7.24 (mult, 6H, Har _yl ) , 3.16 (mult, 7H, OMe and CHMe ₂ ) , 2.48 (mult, 2H, CH ₂ ) , 1.65 (t, 2H, CH ₂ ') , 1.40-1.20 (mult, 24H, CHMe ₂ ) , 0.72 (mult, 2H, CH ₂ ' ' ) .

Example 61 { ^■ [ (2 , 6-i- PrPh) ₂ DABMe ₂ ] Pd (CH ₂ CH ₂ CH ₂ C0 ₂ Me) } [B (C ₆ F ₅ ) ₃ C1]

[ (2, 6-i-PrPh) ₂ DABMe ₂ ] PdMeCl (0.038 g, 0.067 mmol) and methyl acrylate (0.028 g, 0.33 mmol) were dissolved in CD ₂ C1 ₂ . To this solution was added B(C ₆ F ₅ ) ₃ (0.036

, 0.070 mmol) . ^X H NMR of the resulting reaction mixture showed formation of the title compound.

Example 62 A 100 mL autoclave was charged with chloroform (50 mL) , { [(2-t-BuPh) ₂ DABMe ₂ ] PdMe (NCMe) }SbF ₆ " (0.090 g, 0.12 mmol), and ethylene (2.1 MPa) . The reaction mixture was stirred at 25°C and 2.1 MPa ethylene for 3 h. The ethylene pressure was then vented and volatiles removed from the reaction mixture in vacuo to afford 2.695 g of branched polyethylene. The number average molecular weight (M _n ) , calculated by ^X H NMR integration of aliphatic vs. olefinic resonances, was 1600. The degree of polymerization, DP, was calculated on the basis of the ^λ K NMR spectrum to be 59; for a linear polymer this would result in 18 methyl-ended branches per 1000 methylenes. However, based on the ^X H NMR spectrum the number of methyl-ended branches per 1000 methylenes was calculated to be 154. Therefore, it may be concluded that this material was branched polyethylene. *H NMR (CDC1 ₃ ) δ 5.38 (mult, vinyl H's), 1.95 (mult, allylic methylenes), 1.62 (mult, allylic methyls) , 1.24 (mult, non-allylic methylenes and methines) , 0.85 (mult, non-allylic methyls) .

Example 63 A suspension of { [(2-t-

BuPh) ₂ DABMe ₂ ] PdMe (NCMe) }SbF ₆ ^" (0.015 g, 0.02 mmol) in 5 mL FC-75 was agitated under 2.8 MPa of ethylene for 30 min. The pressure was then increased to 4.1 MPa and maintained at this pressure for 3 h. During this time the reaction temperature varied between 25 and 40°C. A viscous oil was isolated from the reaction mixture by decanting off the FC-75 and dried in vacuo . The number average molecular weight (M _n ) , calculated by ^X H NMR integration of aliphatic vs. olefinic resonances, was 2600. DP for this material was calculated on the basis of the ² H NMR spectrum to be 95; for a linear polymer this would result in 11 methyl-ended branches per 1000 methylenes. However, based on the ^X H NMR

spectrum the number of methyl-ended branches per 1000 methylenes was calculated to be 177.

Example 64 A 100 mL autoclave was charged with chloroform (55 mL) , { [ (2-PhPh) ₂ DABMe ₂ ] PdMe (NCMe) }SbF ₆ ^" (0.094 g, 0.12 mmol) , and ethylene (2.1 MPa) . The reaction mixture was stirred at 25°C and 2.1 MPa ethylene for 3 h. The ethylene pressure was then vented and volatiles removed from the reaction mixture in vacuo to afford 2.27 g of a pale yellow oil. Mn was calculated on the basis of ^X H NMR integration of aliphatic vs. olefinic resonances to be 200. The degree of polymerization, DP, was calculated on the basis of the ¹ H NMR spectrum to be 7.2; for a linear polymer this would result in 200 methyl-ended branches per -1000 methylenes. However, based on the E NMR spectrum the number of methyl-ended branches per 1000 methylenes was calculated to be 283.

Example 65

A suspension of [ (2-PhPh) ₂ DABMe ₂ ] PdMe (NCMe) }SbF ₆ ^" (0.016 g, 0.02 mmol) in 5 mL FC-75 was agitated under 1.4 MPa of ethylene for 3 h 40 min. During this time the reaction temperature varied between 23 and 1°C. A viscous oil (329 mg) was isolated from the reaction mixture by decanting off the FC-75 and dried in vacuo . Mn was calculated on the basis of ⁱ H NMR integration of aliphatic vs. olefinic resonances to be 700. The degree of polymerization, DP, was calculated on the basis of the ^X H NMR spectrum to be 24.1; for a linear polymer this would result in 45 methyl-ended branches per 1000 methylenes. However, based on the ^X H NMR spectrum the number of methyl-ended branches per 1000 methylenes was calculated to be 173.

Example 66 A 100 L autoclave was charged with FC-75 (50 mL) , { (Ph ₂ DABMe ) PdMe (NCMe) }SbF ₆ ^" (0.076 g, 0.12 mmol) and ethylene (2.1 MPa) . The reaction mixture was stirred at 24°C for 1.5 h. The ethylene pressure was then vented, and the FC-75 mixture removed from the reactor.

i small amount of insoluble oil was isolated from the mixture by decanting off the FC-75. The reactor was washed out with 2 x 50 mL CHC1 ₃ , and the washings added to the oil. Volatiles removed from the resulting solution in vacuo to afford 144 mg of an oily solid.

Mn was calculated on the basis of ^X H NMR integration of aliphatic vs. olefinic resonances to be 400. The degree of polymerization, DP, was calculated on the basis of the ⁱ H NMR spectrum to be 13.8; for a linear polymer this would result in 83 methyl-ended branches per 1000 methylenes. However, based on the ^X H NMR spectrum the number of methyl-ended branches per 1000 methylenes was calculated to be 288.

Example 67 A 100 mL autoclave was charged with chloroform (50 mL) , { [ (2,6-EtPh) ₂ DABMe ₂ ] PdMe (NCMe) }BAF ^" (0.165 g, 0.12 mmol) , and ethylene (2.1 MPa) . The reaction mixture was stirred under 2.1 MPa of ethylene for 60 min; during this time the temperature inside the reactor increased from 22 to 48°C. The ethylene pressure was then vented and volatiles removed from the reaction mixture in vacuo to afford 15.95 g of a viscous oil. ^X H NMR of this material showed it to be branched polyethylene with 135 methyl-ended branches per 1000 methylenes. GPC analysis in trichlorobenzene (vs. a linear polyethylene standard) gave M _n = 10,400, M _w = 22,100.

Example 66 This was run identically to Example 67, but with { [ (2,6-EtPh) ₂ DABMe ₂ ]PdMe(NCMe) }SbF ₆ ^' (0.090 g, 0.12 mmol) in place of the corresponding BAF salt. The temperature of the reaction increased from 23 to 30°C during the course of the reaction. 5.25 g of a viscous oil was isolated, ^X H NMR of which showed it to be branched polyethylene with 119 methyl-ended branches per 1000 methylenes.

Example 69 A suspension of { [ (Np) ₂ DABMe ] PdMe (NCMe) }SbF ₆ ^" (0.027 g, 0.02 mmol) in 5 mL FC-75 was agitated under 1.4 MPa of ethylene for 3 h; during this time the temperature inside the reactor varied between 25 and 40°C. Two FC-75 insoluble fractions were isolated from the reaction mixture. One fraction, a non-viscous oil floating on top of the FC-75, was removed by pipette and shown by ⁱ H NMR to be branched ethylene oligomers for which M _n = 150 and with 504 methyl-ended branches per 1000 methylenes. The other fraction was a viscous oil isolated by removing FC-75 by pipette; it was shown by ^X H NMR to be polyethylene for which M _n = 650 and with 240 methyl-ended branches per 1000 methylenes. Example 70

A suspension of ( [ (Ph ₂ CH) ₂ DABH ₂ ] PdMe (NCMe) }SbF ₆ ^" (0.016 g, 0.02 mmol) in 5 mL FC-75 was agitated under 1.4 MPa of ethylene for 3 h 40 min. During this time the reaction temperature varied between 23 and 41°C. A viscous oil (43 mg) was isolated from the reaction mixture by decanting off the FC-75 and dried in vacuo . Mn was calculated on the basis of ^X H NMR integration of aliphatic vs. olefinic resonances to be approximately 2000. The degree of polymerization, DP, was calculated on the basis of the ⁱ H NMR spectrum to be 73; for a linear polymer this would result in 14 methyl-ended branches per 1000 methylenes. However, based on the ² H NMR spectrum the number of methyl-ended branches per 1000 methylenes was calculated to be 377. Example 7i

A 100 mL autoclave was charged with FC-75 (50 mL) , <{Ph ₂ DAB (cyclo -CMe ₂ CH ₂ CMe ₂ -) }PdMe (MeCN) )BAF ^" (0.160 g, 0.12 mmol) and ethylene (2.1 MPa) . The reaction mixture was stirred at 24-25°C for 3.5 h. The ethylene pressure was then vented, and the cloudy FC-75 mixture removed from the reactor. The FC-75 mixture was extracted with chloroform, and the chloroform extract concentrated to dryness affording 0.98 g of an oil. Mn

. /as calculated on the basis of ^X H NMR integration of aliphatic vs. olefinic resonances to be 500. The degree of polymerization, DP, was calculated on the basis of the ⁱ H NMR spectrum to be 19.5; for a linear polymer this would result in 57 methyl-ended branches per 1000 methylenes. However, based on the ^X H NMR spectrum the number of methyl-ended branches per 1000 methylenes was calculated to be 452.

Example 72 A 100 mL autoclave was charged with FC-75 (50 mL) , { [ (4-NMe ₂ Ph) ₂ DABMe ₂ ] PdMe (MeCN) }SbF ₆ ^" (MeCN) (0.091 g, 0.12 mmol) and ethylene (2.1 MPa) . The reaction mixture was stirred at 24°C for 1.5 h. The ethylene pressure was then vented, and the cloudy FC-75 mixture removed from the reactor. • The FC-75 was extracted with 3 x 25 mL of chloroform. The reactor was washed out with 3 x 40 mL CHCI ₃ , and the washings added to the extracts. Volatiles removed from the resulting solution in vacuo to afford 556 mg of an oil. Mn was calculated on the basis of ^X H NMR integration of aliphatic vs. olefinic resonances to be 200. The degree of polymerization, DP, was calculated on the basis of the ^X H NMR spectrum to be 8.4; for a linear polymer this would result in 154 methyl-ended branches per 1000 methylenes. However, based on the ^X H NMR spectrum the number of methyl-ended branches per 1000 methylenes was calculated to be 261.

Example 73 Under nitrogen, a 250 mL Schlenk flask was charged with 10.0 g of the monomer CH ₂ =CHC0 ₂ CH ₂ CH ₂ (CF ₂ ) _n CF ₃ (avg n = 9) , 40 mL of methylene chloride, and a magnetic stirbar. To the rapidly stirred solution was added [ (2,6-i-PrPh) DABMe ₂ ]PdMe(OEt ₂ ) }SbF ₆ ^" (0.075 g, 0.089 mmol) in small portions. The resulting yellow-orange solution was stirred under 1 atm of ethylene for 18 h. The reaction mixture was then concentrated, and the viscous product extracted with - 300 mL of petroleum ether. The yellow filtrate was concentrated to

dryness, and extracted a second time with ~ 150 mL petroleum ether. - 500 mL of methanol was added to the filtrate; the copolymer precipitated as an oil which adhered to the sides of the flask, and was isolated by decanting off the petroleum ether/ methanol mixture.

The copolymer was dried, affording 1.33 g of a slightly viscous oil. Upon standing for several hours, an additional 0.70 g of copolymer precipitated from the petroleum ether/ methanol mixture. By ^X H NMR integration, it was determined that the acrylate content of this material was 4.2 mole%, and that it contained 26 ester and 87 methyl-ended branches per 1000 methylenes. GPC analysis in tetrahydrofuran (vs. a PMMA standard) gave M _n = 30,400, M _w = 40,200. iH NMR. (CDC1 ₃ ) δ 4.36 (t, CH ₂ CH ₂ C02CH ₂ CH ₂ R _f ) , 2.45 (mult,

CH ₂ CH ₂ C02CH ₂ CH ₂ R _f ) , 2.31 (t, CH ₂ CH ₂ C02CH ₂ CH ₂ R _f ) , 1.62 (mult, CH ₂ CH ₂ C02CH ₂ CH ₂ R _f ) , 1.23 (mult, other methylenes and methines) , 0.85 (mult, methyls) . ¹³ C NMR gave branching per 1000 CH ₂ : Total methyls (91.3) , Methyl (32.8) , Ethyl (20) , Propyl (2.2) , Butyl (7.7) , Amyl

(2.2) , ≥Hex and end of chains (22.1) . GPC analysis in THF gave Mn = 30,400, Mw = 40,200 vs. PMMA.

Example 74 A 100 mL autoclave was charged with Pd(CH ₃ CH ₂ CN) ] (BF ) ₂ (0.058 g, 0.12 mmol) and chloroform (40 mL) . To this was added a solution of [ 2 , 6-i-PrPh) ₂ DABMe ₂ (0.070 g, 0.17 mmol) dissolved in 10 mL of chloroform under ethylene pressure (2.1 MPa) . The pressure was maintained at 2.1 MPa for 1.5 h, during which time the temperature inside the reactor increased from 22 to 35°C. The ethylene pressure was then vented and the reaction mixture removed from the reactor. The reactor was washed with 3 x 50 mL of chloroform, the washings added to the reaction mixture, and volatiles removed from the resulting solution in vacuo to afford 9.77 g of a viscous oil. ^X H NMR of this material showed it to be branched polyethylene with 96 methyl-ended branches per 1000 methylenes.

Example 75 A 100 mL autoclave was charged with [Pd(CH ₃ CN) ₄ ] (BF ) ₂ (0.053 g, 0.12 mmol) and chloroform (50 mL) . To this was added a solution of (2,6-i- PrPh) ₂ DABMe ₂ (0.070 g, 0.17 mmol) dissolved in 10 mL of chloroform under ethylene pressure (2.1 MPa) . The pressure was maintained at 2.1 MPa for 3.0 h, during which time the temperature inside the reactor increased from 23 to 52°C. The ethylene pressure was then vented and the reaction mixture removed from the reactor. The reactor was washed with 3 x 50 mL of chloroform, the washings added to the reaction mixture, and volatiles removed from the resulting solution in vacuo to afford 25.98 g of a viscous oil. ^X H NMR of this material showed it to be branched polyethylene with 103 methyl- ended branches per 1000 methylenes. GPC analysis in trichlorobenzene gave M _n = 10,800, M _w = 21,200 vs. linear polyethylene.

Example 76 A mixture of 20 mg (0.034 mmol) of [(2,6-i-

PrPh)DABH ₂ ]NiBr ₂ and 60 mL dry, deaerated toluene was magnetically-stirred under nitrogen in a 200-mL three- necked flask with a gas inlet tube, a thermometer, and a gas exit tube which vented through a mineral oil bubbler. To this mixture, 0.75 mL (65 eq) of 3M poly(methylalumoxane) (PMAO) in toluene was added via syringe. The resulting deep blue-black catalyst solution was stirred as ethylene was bubbled through at about 5 ml and 1 atm for 2 hr. The temperature of the mixture rose to 60°C in the first 15 min and then dropped to room temperature over the course of the reaction.

The product solution was worked up by blending with methanol; the resulting white polymer was washed with 2N HCl, water, and methanol to yield after drying (50°C/vacuum/nitrogen purge) 5.69g (6000 catalyst turnovers) of polyethylene which was easily-soluble in hot chlorobenzene. Differential scanning calorimetry

.exhibited a broad melting point at 107°C (67 J/g) . Gel permeation chromatography (trichlorobenzene, 135°C, polystyrene reference, results calculated as polyethylene using universal calibration theory) : M _n =22,300; M _w =102,000; M _w /M _n =4.56. ¹³ C NMR analysis: branching per 1000 CH ₂ : total Methyls (60) , Methyl (41) , Ethyl (5.8) , Propyl (2.5) , Butyl (2.4) , Amyl (1.2) , ≥Hexyl and end of chain (5) ; chemical shifts were referenced to the solvent: the high field carbon of 1, 2,4-trichlorobenzene (127.8 ppm) . A film of polymer (pressed at 200°C) was strong and could be stretched and drawn without elastic recovery.

Example 7

In a Parr ® 600-mL stirred autoclave under nitrogen was combined 23 mg (0.039 mmol) of [(2,6-i- PrPh)DABH ₂ ]NiBr ₂ , 60 mL of dry toluene, and 0.75 mL of poly(methylalumoxane) at 28°C. The mixture was stirred, flushed with ethylene, and pressurized to 414 kPa with ethylene. The reaction was stirred at 414 kPa for 1 hr; the internal temperature rose to 31°C over this time. After 1 hr, the ethylene was vented and 200 mL of methanol was added with stirring to the autoclave. The resulting polymer slurry was filtered; the polymer adhering to the autoclave walls and impeller was scraped off and added to the filtered polymer. The product was washed with methanol and acetone and dried (80°C/vacuum/nitrogen purge) to yield 5.10g (4700 catalyst turnovers) of polyethylene. Differential scanning calorimetry exhibited a melting point at 127°C (170 J/g) . Gel permeation chromatography (trichlorobenzene, 135°C, polystyrene reference, results calculated as polyethylene using universal calibration theory) : M _n =49,300; M _w =123,000; _w /M _n =2.51. Intrinsic viscosity (trichlorobenzene, 135°C) : 1.925 dL/g. Absolute molecular weight averages corrected for branching: M _n =47,400; M _w =134,000; M _w /M _n =2.83. ¹³ C NMR analysis; branching per 1000 CH ₂ : total Methyls (10.5) , Methyl (8.4) , Ethyl (0.9) , Propyl

. (0) , Butyl (0) , ≥Butyl and end of chain (1.1) ; chemical shifts were referenced to the solvent: the high field carbon of 1, 2, 4-trichlorobenzene (127.8 ppm) . A film of polymer (pressed at 200°C) was strong and stiff and could be stretched and drawn without elastic recovery. This polyethylene is much more crystalline and linear than the polymer of Example 76. This example shows that only a modest pressure increase from 1 atm to 414 kPa allows propagation to successfully compete with rearrangement and isomerization of the polymer chain by this catalyst, thus giving a less-branched, more- crystalline polyethylene.

Example 78 A mixture of 12 mg (0.020 mmol) of [(2,6-i- PrPh) DABH ₂ ]NiBr ₂ and 40 mL -dry, deaerated toluene was magnetically-stirred under nitrogen at 15°C in a 100-mL three-necked flask with an addition funnel, a thermometer, and a nitrogen inlet tube which vented through a mineral oil bubbler. To this mixture, 0.5 mL of poly(methylalumoxane) in toluene was added via syringe; the resulting burgundy catalyst solution was stirred for 5 min and allowed to warm to room temperature. Into the addition funnel was condensed (via a Dry Ice condenser on the top of the funnel) 15 mL (about lOg) of cis-2-butene. The catalyst solution was stirred as the cis-2-butene was added as a liquid all at once, and the mixture was stirred for 16 hr. The product solution was treated with 1 mL of methanol and was filtered through diatomaceous earth; rotary evaporation yielded 0.35g (300 catalyst turnovers) of a light yellow grease, poly-2-butene. ^C NMR analysis; branching per 1000 CH ₂ : total Methyls (365), Methyl (285) , Ethyl (72) , ≥Butyl and end of chain (8) ; chemical shifts were referenced to the solvent chloroform-di (77 ppm) .

Listed below are the ¹³ C NMR data upon which the above analysis is based.

177

13C NMR Data

CDCI3, RT, 0.05M CnAcAc

Freq ppm Intensity

41.6071 11.2954

41.1471 13.7193

38.6816 3.55568

37.1805 7.07882

36.8657 33.8859

36.7366 35.1101

36.6196 33.8905

36.2645 12.1006

35.9094 13.3271

35.8004 11.8845

35.5785 4.20104

34.7351 24.9682

34.4325 39.3436

34.3114 59.2878

34.1177 125.698

33.9886 121.887

33.8837 120.233

33.5326 49.8058

33.004 132.842

32.7377 51.2221

32.657 55.6128

32.3705 18.1589

31.5876 9.27643

31.3818 16.409

31.0066 15.1861

30.0946 41.098

29.9736 42.8009

29.7072 106.314

29.3602 60.0884

29.2512 35.0694

29.114 26.6437

28.9769 29.1226

27.9358 3.57351

27.7501 3.56527

27.0682 14.6121

26.7333 81.0769

26.3257 14.4591

26.015 11.8399

25.3008 8.17451

25.0627 5.98833

22.4801 3.60955 2B ₄

22.3308 10.4951 2B ₅ +, EOC

19.6192 90.3272 IBl

19.4618 154.354 lBi

19.3085 102.085 IBl

18.9937 34.7667 iBl

18.8525 38.7651 iBl

13.7721 11.2148 1B ₄ +, EOC, 1B ₃

11.0484 54.8771 1B

10.4552 10.8437 1B ₂

10.1283 11.0735 1B ₂

9.99921 9.36226 IB,

Example 79

A mixture of 10 mg (0.017 mmol) of [(2,6-i- PrPh)DABH ₂ ]NiBr ₂ and 40 mL dry, deaerated toluene was magnetically-stirred under nitrogen at 5°C in a 100-mL three-necked flask with an addition funnel, a thermometer, and a nitrogen inlet tube which vented through a mineral oil bubbler. To this mixture, 0.5 mL of 3M poly(methylalumoxane) in toluene was added via syringe; the resulting burgundy catalyst solution was stirred at 5°C for 40 min. Into the addition funnel was condensed (via a Dry Ice condenser on the top of the funnel) 20 mL (about 15 g) of l-butene. The catalyst solution was stirred as the l-butene was added as a liquid all at once. -The reaction temperature rose to 50°C over 30 min and then dropped to room temperature as the mixture was stirred for 4 hr. The product solution was treated with 1 mL of methanol and was filtered through diatomaceous earth; rotary evaporation yielded 6.17 g (1640 catalyst turnovers) of clear, tacky poly-1-butene rubber. Gel permeation chromatography (trichlorobenzene, 135°C, polystyrene reference, results calculated as polyethylene using universal calibration theory) : M _n =64,700; M _w =115,000; M _w /M _n =1.77. ¹³ C NMR analysis; branching per 1000 CH ₂ : total Methyls (399) , Methyl (86) , Ethyl (272) , ≥Butyl and end of chain (41) ; chemical shifts were referenced to the solvent chloroform-dχ (77 ppm) . This example demonstrates the polymerization of an alpha-olefin and shows the differences in branching between a polymer derived from a 1-olefin (this example) and a polymer derived from a 2-oiefin (Example 78) . This difference shows that the internal oiefin of Example 78 is not first isomerized to an alpha-olefin before polymerizing; thus this catalyst is truly able to polymerize internal olefins.

Listed below are the ¹³ C NMR data upon which the above analysis is based.

2E0C

A 22-mg (0.037-mmol) sample of [(2,6-i- PrPh) DABH ₂ ] NiBr ₂ was introduced into a 600-mL stirred Parr® autoclave under nitrogen. The autoclave was sealed and 75 mL of dry, deaerated toluene was introduced into the autoclave via gas tight syringe through a port on the autoclave head. Then 0.6 mL of 3M poly (methylalumoxane) was added via syringe and stirring was begun. The autoclave was pressurized with

-.ropylene to 414 kPa and stirred with continuous propylene feed. There was no external cooling. The internal temperature quickly rose to 33°C upon initial propylene addition but gradually dropped back to 24°C over the course of the polymerization. After about 7 min, the propylene feed was shut off and stirring was continued; over a total polymerization time of 1.1 hr, the pressure dropped from 448 kPa to 358 kPa. The propylene was vented and the product, a thin, honey- colored solution, was rotary evaporated to yield 1.65g of a very thick, brown semi-solid. This was dissolved in chloroform and filtered through diatomaceous earth; concentration yielded 1.3 g (835 catalyst turnovers) of tacky, yellow polypropylene rubber. Gel permeation chromatography (trichlorobenzene, 135°C, polystyrene reference, results calculated as polypropylene using universal calibration theory) : M _n =7,940; M _w =93,500; M _w /M _n =11.78.

Example 81 A mixture of 34 mg (0.057 mmol) of [(2,6-i-

PrPh)DABH ₂ ]NiBr ₂ and 20 mL dry, deaerated toluene was magnetically-stirred under nitrogen at 5°C in a 100-mL three-necked flask with a thermometer and a nitrogen inlet tube which vented through a mineral oil bubbler. To this mixture, 0.7 mL of 3M poly(methylalumoxane) in toluene was added via syringe and the resulting deep blue-black solution was stirred for 30 min at 5°C. To this catalyst solution was added 35 mL of dry, deaerated cyclopentene, and the mixture was stirred and allowed to warm to room temperature over 23 hr. The blue-black mixture was filtered through alumina to remove dark blue-green solids (oxidized aluminum compounds from PMAO) ; the filtrate was rotary evaporated to yield 1.2 g (310 catalyst turnovers) of clear liquid cyclopentene oligomers.

Exampl 82 A 20-mg (0.032 mmol) sample of [(2,6-i- PrPh)DABMe ₂ ]NiBr ₂ was placed in Parr® 600-mL stirred

autoclave under nitrogen. The autoclave was sealed and 100 mL of dry, deaerated toluene and 0.6 mL of 3M poly(methylalumoxane) were injected into the autoclave through the head port, and mixture was stirred under nitrogen at 20°C for 50 min. The autoclave body was immersed in a flowing water bath and the autoclave was then pressurized with ethylene to 2.8 MPa with stirring as the internal temperature rose to 53°C. The autoclave was stirred at 2.8 MPa (continuous ethylene feed) for 10 min as the temperature dropped to 29°C, and the ethylene was then vented. The mixture stood at 1 atm for 10 min; vacuum was applied to the autoclave for a few minutes and then the autoclave was opened. The product was a stiff, swollen polymer mass which was scraped out, cut. up, and fed in portions to 500 mL methanol in a blender. The polymer was then boiled with a mixture of methanol (200 mL) and trifiuoroacetic acid (10 mL) , and finally dried under high vacuum overnight to yield 16.8g (18,700 catalyst turnovers) of polyethylene. The polymer was somewhat heterogeneous with respect to crystallinity, as can be seen from the differential scanning calorimetry data below; amorphous and crystalline pieces of polymer could be picked out of the product. Crystalline polyethylene was found in the interior of the polymer mass,- amorphous polyethylene was on the outside. The crystalline polyethylene was formed initially when the ethylene had good access to the catalyst; as the polymer formed limited mass transfer, the catalyst became ethylene-starved and began to make amorphous polymer. Differential scanning calorimetry: (crystalline piece of polymer) : mp: 130°C (150J/g) ; (amorphous piece of polymer) : -48°C (Tg) ,- mp: 42°C (3J/g) , 96°C (llJ/g) . Gel permeation chromatography (trichlorobenzene, 135°C, polystyrene reference, results calculated as polyethylene using universal calibration theory) : M _n =163,000; M _w =534,000; M _w /M _r .=3.27. This example demonstrates the effect of

ethylene mass transfer on the polymerization and- shovs that the same catalyst can make both amorphous and crystalline polyethylene. The bulk of the polymer was crystalline: a film pressed at 200°C was tough and stiff.

Example 83 A 29-mg (0.047 mmol) sample of [(2,6-i- PrPh)DABMe ₂ ]NiBr ₂ was placed in Parr® 600-mL stirred autoclave under nitrogen. The autoclave was sealed and 100 mL of dry, deaerated toluene and 0.85 mL of 3M poly(methylalumoxane) were injected into the autoclave through the head port. The mixture was stirred under nitrogen at 23°C for 30 min. The autoclave body was immersed in a flowing water bath and the autoclave was pressurized with ethylene to 620 kPa with stirring. The internal temperature peaked at 38°C within 2 min. The autoclave was stirred at 620 kPa (continuous ethylene feed) for 5 min as the temperature dropped to 32°C. The ethylene was then vented, the regulator was readjusted, and the autoclave was pressurized to 34.5 kPa (gauge) and stirred for 20 min (continuous ethylene feed) as the internal temperature dropped to 22°C. In the middle of this 20 min period, the ethylene feed was temporarily shut off for 1 min, during which time the autoclave pressure dropped from 34.5 kPa (gauge) to 13.8 kPa; the pressure was then restored to 34.5 kPa. After stirring 20 min at 34.5 kPa, the autoclave was once again pressurized to 620 kPa for 5 min; the internal temperature rose from 22°C to 34°C. The ethylene feed was shut off for about 30 sec before venting; the autoclave pressure dropped to about 586 kPa.

The ethylene was vented; the product was a dark, thick liquid. Methanol (200 mL) was added to the autoclave and the mixture was stirred for 2 hr. The polymer, swollen with toluene, had balled up on the stirrer, and the walls and bottom of the autoclave were coated with white, fibrous rubbery polymer. The

183

polymer was scraped out, cut up, and blended with methanol in a blender and then stirred with fresh boiling methanol for 1 hr. The white rubber was dried under high vacuum for 3 days to yield 9.6 g (7270 catalyst turnovers) of rubbery polyethylene. ¹ H NMR analysis (CDCI3) : 95 methyl carbons per 1000 methylene carbons .

Differential scanning calorimetry: -51°C (Tg) ; mp.- 39.5°C (4J/g) ; mp: 76.4°C (7J/g) . Gel permeation chromatography (trichlorobenzene, 135°C, polystyrene reference, results calculated as polyethylene using universal calibration theory) : M _n =223,000; M _w =487,000; M _w /M _n =2.19.

The polyethylene of Example 83 could be cast from hot chlorobenzene or press-ed at 200°C to give a strong, stretchy, hazy, transparent film with good recovery. It was not easily chloroform-soluble. This example demonstrates the use of the catalyst's ability (see Example 82) to make both amorphous and crystalline polymer, and to make both types of polymer within the same polymer chain due to the catalyst's low propensity to chain transfer. With crystalline blocks (due to higher ethylene pressure) on both ends and an amorphous region (due to lower- pressure, mass transfer-limited polymerization) in the center of each chain, this polymer is a thermoplastic elastomer.

Example 84 A Schlenk flask containing 147 mg (0.100 mmol) of { [ (2, 6-i-PrPh)DABMe ₂ ] PdMe(0Et ₂ ) }BAF ^" was cooled to - 78°C, evacuated, and placed under an ethylene atmosphere. Methylene chloride (100 ml) was added to the flask and the solution was then allowed to warm to room temperature and stirred. The reaction vessel was warm during the first several hours of mixing and the solution became viscous. After being stirred for 17.4 h, the reaction mixture was added to -600 mL of MeOH in order to precipitate the polymer. Next, the MeOH was decanted off of the sticky polymer, which was then

dissolved in -600 mL of petroleum ether. After being filtered through plugs of neutral alumina and silica gel, the solution appeared clear and almost colorless. The solvent was then removed and the viscous oil (45.31 g) was dried in vacuo for several days: ^X H NMR (CDCI ₃ , 400 MHz) δ 1.24 (CH ₂ , CH) , 0.82 (m, CH ₃ ) ; Branching: -128 CH ₃ per 1000 CH ₂ ; DSC: T _g = -67.7°C. GPC: Mn = 29, 000; Mw = 112, 000.

Example 85 Following the procedure of Example 84 { [(2,6-i- PrPh) DABMe ₂ ] PdMe (OEt ₂ ) }BAF ^" (164 mg, 0.112 mmol) catalyzed the polymerization of ethylene for 24 h in 50 mL of CH ₂ C1 ₂ to give 30.16 g of polymer as a viscous oil. ⁱ H NMR (C ₆ D ₆ ) δ 1.41 (CH ₂ , CH) , 0.94 (CH ₃ ) ; Branching: -115 CH ₃ per 1000 CH ₂ ; GPC Analysis (THF, PMMA standards, RI Detector) : M _w = 262,000; M _n = 121,000; PDI = 2.2; DSC: T _g = -66.8°C.

Example 86 The procedure of Example 84 was followed using 144 mg (0.100 mmol) of { [ (2, 6-i-PrPh)DABH ₂ ] PdMe (OEt ₂ ) }BAF ^" in 50 mL of CH ₂ C1 ₂ and a 24 h reaction time. Polymer (9.68 g) was obtained as a free-flowing oil. ^X H NMR (CDCI ₃ , 400 MHz) δ 5.36 (m, RHC=CHR') , 5.08 (br s, RR'C=CHR' ') , 4.67 (br s, H ₂ C=CRR') , 1.98 (m, allylic H) , 1.26 (CH ₂ , CH) , 0.83 (m, CH ₃ ); Branching: -149 CH ₃ per 1000 CH ₂ ; DSC: T _g = -84.6°C.

Example 87 A 30-mg (0.042-mmol) sample of [(2,6-i- PrPh) DABAn]NiBr ₂ was placed in Parr® 600-mL stirred autoclave under nitrogen. The autoclave was sealed and 150 mL of dry toluene and 0.6 mL of 3M polymethylalumoxane were injected into the autoclave through the head port . The autoclave body was immersed in a flowing water bath and the mixture was stirred under nitrogen at 20°C for 1 hr. The autoclave was then pressurized with ethylene to 1.31 MPa with stirring for 5 min as the internal temperature peaked at 30°C. The ethylene was then vented to 41.4 kPa

_ (gauge) and the mixture was stirred and fed ethylene at 41.4 kPa for 1.5 hr as the internal temperature dropped to 19°C. At the end of this time, the autoclave was again pressurized to 1.34 MPa and stirred for 7 min as the internal temperature rose to 35°C.

The ethylene was vented and the autoclave was briefly evacuated; the product was a stiff, solvent- swollen gel. The polymer was cut up, blended with 500 mL methanol in a blender, and then stirred overnight with 500 mL methanol containing 10 mL of 6N HCl. The stirred suspension in methanol/HCl was then boiled for 4 hr, filtered, and dried under high vacuum overnight to yield 26.1 g (22,300 catalyst turnovers) of polyethylene. Differential scanning calorimetry: -49°C (Tg) ; mp: 116°C (42J/g) . The melting transition was very broad and appeared to begin around room temperature. Although the melting point temperature is higher in this Example than in Example 76, the area under the melting endotherm is less in this example, implying that the polymer of this Example is less crystalline overall, but the crystallites that do exist are more ordered. This indicates that the desired block structure was obtained. Gel permeation chromatography (trichlorobenzene, 135°C, polystyrene reference, results calculated as polyethylene using universal calibration theory) : M _n =123,000; M _w =601,000; M _w /M _n = .87. The polyethylene of this example could be pressed at 200°C to give a strong, tough, stretchy, hazy film with partial elastic recovery. When the stretched film was plunged into boiling water, it completely relaxed to its original dimensions.

Example B8 A 6.7-mg (0.011-mmol) sample of [(2,6-i- PrPh) DABMe ₂ ]NiBr ₂ was magnetically-stirred under nitrogen in a 50-mL Schlenk flask with 25 mL of dry, deaerated toluene as 0.3 mL of 3M poly(methylalumoxane) was injected via syringe. The mixture was stirred at 23°C for 40 min to give a deep blue-green solution of

. atalyst. Dry, deaerated cyclopentene (10 mL) was injected and the mixture was stirred for 5 min. The flask was then pressurized with ethylene at 20.7 MPa and stirred for 22 hr. The resulting viscous solution was poured into a stirred mixture of 200 mL methanol and 10 mL 6N HCl. The methanol was decanted off and replaced with fresh methanol, and the polymer was stirred in boiling methanol for 3 hr. The tough, stretchy rubber was pressed between paper towels and dried under vacuum to yield 1. Og of poly[ethylene/cyclopentene] . By ^-H NMR analysis (CDCI3) : 100 methyl carbons per 1000 methylene carbons . Comparison of the peaks attributable to cyclopentene (0.65 ppm and 1.75 ppm) with the standard polyethylene peaks (0.9 ppm and 1.3 ppm) indicates about a 10 mol% cyclopentene incorporation. This polymer yield and composition represent about 2900 catalyst turnovers. Differential scanning calorimetry: -44°C (Tg) . Gel permeation chromatography (trichlorobenzene, 135°C, polystyrene reference, results calculated as polyethylene using universal calibration theory) : M _n =122,000; M _w =241,000; M _w /M _n =1.97.

Listed below are the ¹³ C NMR data upon which the above analysis is based.

¹³ C NMR data

TCB, 120C, 0.05M CrAcAc

Freq ppm Intensity

50.9168 5.96663

46.3865 3.27366 1 cme and/or 1,3 ccmcc

40.7527 40.5963 2 erne

40.567 41.9953 1,3 erne

40.3336 45.8477 1,3 erne

37.1985 60.1003

36.6998 41.2041

36.0579 11.2879

35.607 25.169

34.4771 19.0834

34.0845 22.8886

33.1243 20.1138

32.8962 27.6778

31.8406 75.2391

30.0263 76.2755

29.6921 170.41

28.9494 18.8754

28.647 25.8032

27.4588 22.2397

27.1086 48.0806

24.3236 3.31441

22.5783 4.64411 2B ₅ +, 2 EOC

19.6712 43.1867 lB _χ

17.5546 1.41279 end group

14.3399 1.74854 1B ₃

13.8518 5.88699 1B ₄ +, 1E0C

10.9182 2.17785 2B _χ

Example 89 A 7.5-mg (0.013-mmol) sample of [(2,6-t- BuPh) DABMe ₂ ] NiBr ₂ was magnetically stirred under nitrogen in a 50-mL Schlenk flask with 40 mL of dry, deaerated toluene as 0.5 mL of 3M poly(methylalumoxane) was injected via syringe. - The mixture was stirred at 23°C for 1 hr to give a deep blue-green solution of catalyst. The flask was pressurized with ethylene at 20.7 kPa (gauge) and stirred for 20 hr. The solution, which had become a reddish-brown suspension, was poured into a stirred mixture of 200 mL methanol and 10 mL 6N HCl and was stirred at reflux for 1 hr. The methanol was decanted off and replaced with fresh methanol, and the white polymer was stirred in boiling methanol for 1 hr. The stiff, stretchy rubber was pressed between paper towels and then dried under vacuum to yield 1.25 g (3380 catalyst turnovers) of polyethylene. ¹ H-1 NMR analysis (CgDβ) : 63 methyl carbons per 1000 methylene carbons. Differential scanning calorimetry: -34°C (Tg) ; mp: 44°C (31J/g) ; mp: 101°C (23J/g) .

Example 90 A 5.5 mg (0.0066 mmol) sample of { [(2,6-i- PrPh) ₂ DABMe ₂ ] PdMe (Et ₂ 0) }SbF ₆ ^" was allowed to stand at room temperature in air for 24 hr. A 100-mL three-neck flask with a magnetic stirrer and a gas inlet dip tube was charged with 40 mL of reagent methylene chloride and ethylene gas was bubbled through with stirring to saturate the solvent with ethylene. The sample of { [ (2, 6-i-PrPh) ₂ DABMe ₂ ] PdMe (Et ₂ 0) }SbF ₆ ^" was then rinsed

.into the flask with 5 mL of methylene chloride -and ethylene was bubbled through with stirring for 5 hr. The clear yellow solution was rotary evaporated to yield 0.20 g (1080 catalyst turnovers) of a thick yellow liquid polyethylene.

Example 91 A 600-mL stirred Parr ^® autoclave was sealed and flushed with nitrogen, and 100 mL of dry, deaerated toluene was introduced into the autoclave via gas tight syringe through a port on the autoclave head. The autoclave was purged with propylene gas to saturate the solvent with propylene. Then 45 mg (0.054 mmol) of { [ (2, 6-i-PrPh) ₂ DABMe ₂ ] PdMe (Et ₂ 0) }SbF ₆ ^" was introduced into the autoclave in the following manner: a 2.5-mL gas tight syringe with a syringe valve was loaded with 45 mg of{ [ (2, 6-i-PrPh) ₂ DABMe ₂ ] PdMe (Et ₂ 0) }SbF ₆ ^~ under nitrogen in a glove box; then 1-2 mL of dry, deaerated methylene chloride was drawn up into the syringe and the contents were quickly injected into the autoclave through a head port. This method avoids having the catalyst in solution with no stabilizing ligands.