Alpha-olefins and olefin polymers and processes therefor

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

• 97
• with an olefin wherein:
• said olefin is selected from the group consisting of ethylene, an olefin of the formula R17CH═CH2 or R17CH═CHR17, cyclobutene, cyclopentene, norbornene, or a 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;
• R2 and R5 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;
• R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a carbocyclic ring;
• R44 is hydrocarbyl or substituted hydrocarbyl, and R28 is hydrogen, hydrocarbyl or substituted hydrocarbyl or R44 and R28 taken together form a ring;
• R45 is hydrocarbyl or substituted hydrocarbyl, and R29 is hydrogen, substituted hydrocarbyl or hydrocarbyl, or R45 and R29 taken together form a ring;
• each R30 is independently hydrogen, substituted hydrocarbyl or hydrocarbyl, or two of R30 taken together form a ring;
• R20 and R23 are independently hydrocarbyl or substituted hydrocarbyl;
• R21 and R22 are each in independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
• each R17 is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said olefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms;
• R1 is hydrogen, hydrocarbyl or substituted hydrocarbyl;
• n is 2 or 3;
• and provided that:
• when said bidentate ligand is (XXX) M is not Pd;
• when M is Pd a diene is not present;
• and
• said transition metal also has bonded to it a ligand that may be displaced by said olefin or add to said olefin;
• when norbornene or substituted norbornene is used no other olefin is present.

A process for the copolymerization of an olefin and a fluorinated olefin, comprising, contacting a transition metal complex of a bidentate ligand selected from the group consisting of

• 98
• with an olefin, and a fluorinated olefin wherein:
• said olefin is selected from the group consisting of ethylene and an olefin of the formula R17CH═CH2 or R17CH═CHR17;
• said transition metal is selected from the group consisting of Ni and Pd;
• said fluorinated olefin is of the formula H2C═CH(CH2)aRfR42;
• a is an integer of 2 to 20;
• Rf is perfluoroalkylene optionally containing one or more ether groups;
• R42 is fluorine or a functional group;
• R2 and R5 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;
• R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a carbocyclic ring;
• each R17 is independently saturated hydrocarbyl;
• and provided that said transition metal also has bonded to it a ligand that may be displaced by said olefin or added to said olefin.

A copolymer of an olefin of the formula R17CH═CHR17 and a fluorinated olefin of the formula H2C═CH(CH2)aRfR42, wherein:

• each R17 is independently hydrogen or saturated hydrocarbyl;
• a is an integer of 2 to 20;
• Rf is perfluoroalkylene optionally containing one or more ether groups;
• and
• R42 is fluorine or a functional group;
• provided that when both of R17 are hydrogen and R42 is fluorine, Rf is —(CF2)b— wherein b is 2 to 20 or perfluoroalkylene containing at least one ether group.

A process for the polymerization of olefins, 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 formula
• 99
• and one or more monomers selected from the group consisting of ethylene, an olefin of the formula R17CH═CH2 or R17CH═CHR17, cyclobutene, cyclopentene, substituted norbornene, or norbornene;
• wherein:
• M is Ti, Zr, Sc, V, Cr, a rare earth metal, Fe, Co, Ni or Pd in the m oxidation state;
• y+z=m
• R2 and R5 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;
• R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a carbocyclic ring;
• each R17 is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said olefin 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.

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 olefin of the formula R17CH═CH2 or R17CH═CHR17, cyclobutene, cyclopentene, substituted norbornene, and norbornene;

• and a compound of the formula
• 100
• wherein:
• R2 and R5 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;
• R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a carbocyclic ring;
• T1 is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, R15C(═O)— or R15OC(═O)—;
• 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;
• R15 is hydrocarbyl not containing olefinic or acetylenic bonds;
• each R17 is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said olefin 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 R16 is independently hydrogen or alkyl containing 1 to 10 carbon atoms;
• n is 1, 2, or 3;
• R8 is hydrocarbyl;
• and
• T2 is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, hydrocarbyl substituted with keto or ester groups but not containing olefinic or acetylenic bonds, R15C (═O)— or R15OC(═O)—;
• provided that:
• when M is Pd, or (II) or (VII) are present, a diene is not present;
• and
• when norbornene or substituted norbornene is used no other monomer is present.

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 olefin of the formula R17CH═CH2 or R17CH═CHR17, cyclobutene, cyclopentene, substituted norbornene, and norbornene;

• with a compound of the formula
• 101
• wherein:
• R44 is hydrocarbyl or substituted hydrocarbyl, and R28 is hydrogen, hydrocarbyl or substituted hydrocarbyl or R44 and R28 taken together form a ring;
• R45 is hydrocarbyl or substituted hydrocarbyl, and R29 is hydrogen, substituted hydrocarbyl or hydrocarbyl, or R45 and R29 taken together form a ring;
• each R30 is independently hydrogen, substituted hydrocarbyl or hydrocarbyl or two of R30 taken together form a ring;
• R20 and R23 are independently hydrocarbyl or substituted hydrocarbyl;
• R21and R22 are each in independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
• n is 2 or 3;
• T1 is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, R15C(═O)— or R15OC(═O)—;
• M is Ti, Zr, Sc, Cr, a rare earth metal, V, Fe, Co, Ni or Pd the m oxidation state;
• for (XVII), y+z=m;
• for (XIII), m is 2;
• Q is alkyl, hydride, chloride, iodide, or bromide;
• S is alkyl, hydride, chloride, iodide, or bromide;
• T2 is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, hydrocarbyl substituted with keto or ester groups but not containing olefinic or acetylenic bonds, R15C(═O)— or R15OC(═O)—;
• 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 that:
• when said compound is (XVII) M is not Pd;
• 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.

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 olefin of the formula R17CH═CH2 or R17CH═CHR17, cyclobutene, cyclopentene, substituted norbornene, and norbornene;

• with a compound of the formula
• 102
• wherein:
• R20 and R23 are independently hydrocarbyl or substituted hydrocarbyl;
• R21 and R23 are each in independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
• X is a weakly coordinating anion;
• each R17 is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said olefin 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);
• T2 is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, hydrocarbyl substituted with keto or ester groups but not containing olefinic or acetylenic bonds, R15C(═O)— or R15OC(═O)—;
• 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.

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 formula
• 103
• and one or more monomers selected from the group consisting of ethylene, an olefin of the formula R17CH═CH2 or R17CH═CHR17, 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;
• R44 is hydrocarbyl or substituted hydrocarbyl, and R28 is hydrogen, substituted hydrocarbyl or hydrocarbyl, or R44 and R28 taken together form a ring;
• R45 is hydrocarbyl or substituted hydrocarbyl, and R29 is hydrogen, substituted hydrocarbyl or hydrocarbyl, or R45 and R29 taken together form a ring;
• each R30 is independently hydrogen, substituted hydrocarbyl or hydrocarbyl, or two of R30 taken together form a ring;
• n is 2 or 3;
• y and z are positive integers;
• y+z=m;
• each R17 is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said olefin 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.

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 olefin of the formula R17CH═CH2 or R17CH═CHR17, cyclobutene, cyclopentene, substituted norbornene, and norbornene;

• optionally a source of X−, and a compound of the formula
• 104
• wherein:
• R2 and R5 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;
• R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a carbocyclic ring;
• each R17 is independently hydrocarbyl or substituted hydrocarbyl provided that R17 contains no olefinic bonds;
• T1 is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, R15C(═O)— or R15OC(═O)—;
• R15 is hydrocarbyl not containing olefinic or acetylenic bonds;
• E is halogen or —OR18;
• R18 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.

A process for the polymerization of olefins, 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 formula
• 105
• and one or more monomers selected from the group consisting of ethylene, an olefin of the formula R17CH═CH2 or R17CH═CHR17, 4-vinylcyclohexene, cyclobutene, cyclopentene, substituted norbornene, and norbornene;
• wherein:
• M is Ni(II), Co(II), Fe(II) or Pd(II);
• R2 and R5 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;
• R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a carbocyclic ring;
• each R17 is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said olefin 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, and further provided that when 4-vinylcyclohexene is present M is Ni;
• 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.

A polymerization process, comprising, contacting a compound of the formula [Pd(R13CN)4]X2, or a combination of Pd[OC(O)R40]2 and HX, with a compound of the formula

• 106
• and one or more monomers selected from the group consisting of ethylene, an olefin of the formula R17CH═CH2 or R17CH═CHR17, cyclopentene, cyclobutene, substituted norbornene, and norbornene, wherein:
• R2 and R5 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;
• R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a carbocyclic ring;
• each R17 is independently hydrocarbyl or substituted hydrocarbyl provided R17 contains no olefinic bonds;
• R13 is hydrocarbyl;
• R40 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.

A polymerization process, comprising, contacting:

• a Ni[0], Pd[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
• 107
• an oxidizing agent;
• a source of a relatively weakly coordinating anion;
• and one or more monomers selected from the group consisting of ethylene, an olefin of the formula R17CH═CH2 or R17CH═CHR17, cyclopentene, cyclobutene, substituted norbornene, and norbornene;
• wherein:
• R2 and R5 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;
• R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
• each R17 is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said olefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms;
• each R31 is independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
• R44 is hydrocarbyl or substituted hydrocarbyl, and R28 is hydrogen, hydrocarbyl or substituted hydrocarbyl or R44 and R28 taken together form a ring;
• R45 is hydrocarbyl or substituted hydrocarbyl, and R29 is hydrogen, substituted hydrocarbyl or hydrocarbyl, or R45 and R29 taken together form a ring;
• each R30 is independently hydrogen, substituted hydrocarbyl or hydrocarbyl, or two of R30 taken together form a ring;
• R46 and R47 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;
• n is 2 or 3;
• R48 and R49 are each independently hydrogen, hydrocarbyl, or substituted hydrocarbyl;
• R20 and R23 are independently hydrocarbyl or substituted hydrocarbyl;
• R21 and R22 are each in independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
• and
• provided that;
• when norbornene or substituted norbornene is present, no other monomer is present;
• when a 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.

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

• 108
• and one or more monomers selected from the group consisting of ethylene, an olefin of the formula R17CH═CH2 or R17CH═CHR17, cyclopentene, cyclobutene, substituted norbornene, and norbornene;
• wherein:
• R2 and R5 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;
• R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
• and
• each R17 is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said olefin 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

• 109
• and one or more monomers selected from the group consisting of ethylene, an olefin of the formula R17CH═CH2 or R17CH═CHR17, cyclopentene, cyclobutene, substituted norbornene, and norbornene;
• wherein:
• R2 and R5 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;
• R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
• and
• each R17 is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said olefin 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.

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

• 110
• and one or more monomers selected from the group consisting of ethylene, an olefin of the formula R17CH═CH2 or R17CH═CHR17, cyclopentene, cyclobutene, substituted norbornene, and norbornene;
• wherein:
• R2 and R5 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;
• R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
• each R17 is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said olefin 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.

A process for the polymerization of olefins, 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 formula
• 111
• and one or more monomers selected from the group consisting of ethylene, an olefin of the formula R17CH═CH2 or R17CH═CHR17, cyclobutene, cyclopentene, substituted norbornene, or norbornene;
• wherein:
• M is Ni(II) or Pd(II);
• R20 and R23 are independently hydrocarbyl or substituted hydrocarbyl;
• R21 and R22 are each in independently hydrogen, hydrocarbyl or substituted hydrocarbyl;
• each R17 is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said olefin 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;
• 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.

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

• 112
• and one or more monomers selected from the group consisting of ethylene, an olefin of the formula R17 CH═CH2 or R17CH═CHR17 , cyclopentene, cyclobutene, substituted norbornene, and norbornene;
• wherein:
• R2 and R5 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;
• R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a carbocyclic ring;
• each R17 is independently hydrocarbyl or substituted hydrocarbyl provided that R17 does not contain any olefinic bonds;
• and
• each R27 is independently hydrocarbyl;
• each X is a weakly coordinating anion;
• provided that, when norbornene or substituted norbornene is present, no other monomer is present.

A process for the polymerization of olefins, 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 formula
• 113
• and one or more monomers selected from the group consisting of ethylene, an olefin of the formula R17CH═CH2 or R17CH═CHR17, cyclopentene, cyclobutene, substituted norbornene, and norbornene;
• wherein:
• R46 and R47 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;
• R48 and R49 are each independently hydrogen, hydrocarbyl, or substituted hydrocarbyl;
• each R31 is independently hydrocarbyl, substituted hydrocarbyl, or hydrogen;
• M is Ti, Zr, V, Cr, a rare earth metal, Co, Fe, Sc, Ni, or Pd of oxidation state m;
• y and z are positive integers;
• y+z=m;
• each R17 is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said olefin 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.

A compound of the formula

• 114
• wherein:
• R2 and R5 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;
• R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a carbocyclic ring;
• T1 is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, R15C(═O)— or R1OC(═O)—;
• 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
• R15 is hydrocarbyl not containing olefinic or acetylenic bonds;
• provided that when R3 and R4 taken together are hydrocarbylene to form a carbocyclic ring Z is not an organic nitrile.

A compound of the formula

• 115
• wherein:
• R50 is substituted phenyl;
• R51 is phenyl or substituted phenyl;
• R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
• and provided that groups in the 2 and 6 positions of R50 have a difference in Es of about 0.15 or more.

A compound of the formula

• 116
• wherein:
• R52 is substituted phenyl;
• R53 is phenyl or substituted phenyl;
• R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 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 R52 have a difference in Es of 0.15 or more;
• 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.

A compound of the formula

• 117
• wherein:
• R2 and R5 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;
• R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
• T1 is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, R15C(═O)— or R15OC(═O)—;
• R15 is hydrocarbyl not containing an olefinic or acetylenic bond;
• 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.

A compound of the formula

• 118
• wherein:
• R2 and R5 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;
• R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
• M is Ni(II) or Pd(II);
• each R16 is independently hydrogen or alkyl containing 1 to 10 carbon atoms;
• n is 1, 2, or 3;
• X− is a weakly coordinating anion;
• and
• R8 is hydrocarbyl.

A compound of the formula

• 119
• wherein:
• R2 and R5 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;
• R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
• E is halogen or —OR18;
• R18 is hydrocarbyl not containing olefinic or acetylenic bonds;
• T1 is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, R15C(═O)— or R15OC(═O)—;
• R15 is hydrocarbyl not containing olefinic or acetylenic bonds;
• and
• X− is a weakly coordinating anion.

A compound of the formula [(η4-1,5-COD)PdT1Z]+X−, wherein:

• T1 is hydrocarbyl not containing olefinic or acetylenic bonds;
• X− is a weakly coordinating anion;
• COD is 1,5-cyclooctadiene;
• Z is R10CN;
• and
• R10 is hydrocarbyl not containing olefinic or acetylenic bonds.

A compound of the formula

• 120
• wherein:
• M is Ni(II) or Pd(II);
• R2 and R5 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;
• R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
• each R11 is independently hydrogen, alkyl or —(CH2)mCO2R1;
• T3 is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, or —CH2CH2CH2CO2R8;
• P is a divalent group containing one or more repeat units derived from the polymerization of one or more of ethylene, an olefin of the formula R17CH═CH2 or R17CH═CHR17, cyclobutene, cyclopentene, substituted norbornene, or norbornene and, when M is Pd(II), optionally one or more of:
• a compound of the formula CH2═CH(CH2)mCO2R1, Co, or a vinyl ketone;
• R8 is hydrocarbyl;
• m is 0 or an integer from 1 to 16;
• R1 is hydrogen, or hydrocarbyl or substituted hydrocarbyl containing 1 to 10 carbon atoms;
• and X− is a weakly coordinating anion.

A compound of the formula

• 121
• wherein:
• R2 and R5 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;
• R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
• T2is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, hydrocarbyl substituted with keto or ester groups but not containing olefinic or acetylenic bonds, R15CO(═O)— or R15OC (═O)—;
• R15 is hydrocarbyl not containing olefinic or acetylenic bonds;
• and
• X is a weakly coordinating anion.

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

• 122
• with one or more monomers selected from the group consisting of ethylene, an olefin of the formula R17CH═CH2 or R17CH═CHR17, cyclobutene, cyclopentene, substituted norbornene, and norbornene,
• wherein:
• M is Ni(II) or Pd(II);
• R2 and R5 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;
• R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
• each R11 is independently hydrogen, alkyl or —(CH2)mCO2R1;
• T3 is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, or —CH2CH2CH2CO2R8;
• 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 olefin of the formula R17CH═CH2 or R17 CH═CHR17, cyclopentene, cyclobutene, substituted norbornene, and norbornene, and, when M is Pd(II), optionally one or more of:
• a compound of the formula CH2═CH(CH2)mCO2R1, CO, or a vinyl ketone;
• R8 is hydrocarbyl;
• each R17 is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said olefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms;
• R1 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) R11 is not —CO2R8.

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

• 123
• and one or more monomers selected from the group consisting of ethylene, an olefin of the formula R17CH═CH2 or R17 CH═CHR17, 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 m;
• R2 and R5 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;
• R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
• each R11 is independently hydrogen or alkyl, or both of R11 taken together are hydrocarbylene to form a carbocyclic ring;
• T3 is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, or —CH2CH2CH2CO2R8;
• Q is a monoanion;
• 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 olefin of the formula R17CH═CH2 or R17CH═CHR17, cyclopentene, cyclobutene, substituted norbornene, and norbornene, and, when M is Pd(II), optionally one or more of:
• a compound of the formula CH2═CH(CH2)mCO2R1, CO, or a vinyl ketone;
• R8 is hydrocarbyl;
• a is 1 or 2;
• y+a+1=m;
• each R17 is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said olefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms;
• R1 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), T3 is not —CH2CH2CH2CO2R8.

A compound of the formula

• 124
• wherein:
• M is Zr, Ti, Sc, V, Cr, a rare earth metal, Fe, Co, Ni or Pd of oxidation state m;
• R2 and R5 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;
• R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
• each R11 is independently hydrogen, or alkyl, or both of R11 taken together are hydrocarbylene to form a carbocyclic ring;
• T3 is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, or —CH2CH2CH2CO2R8;
• 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 olefin of the formula R17CH═CH2 or R17CH═CHR17, cyclopentene, cyclobutene, substituted norbornene, and norbornene, and optionally, when M is Pd(II), one or more of:
• a compound of the formula CH2═CH(CH2)mCO2R1, CO, or a vinyl ketone;
• Q is a monovalent anion;
• R8 is hydrocarbyl;
• a is 1 or 2;
• y+a+1=m;
• each R17 is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said olefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms;
• R1 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 diene is not present;.

A process, comprising, contacting, at a temperature of about −40° C. to about +60° C., a compound of the formula [(η4-1,5-COD)PdT1Z]+X− and a diimine of the formula

• 125
• to produce a compound of the formula
• 126
• wherein:
• T1 is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, R15C(═O)— or R15OC(═O)—;
• X is a weakly coordinating anion;
• COD is 1,5-cyclooctadiene;
• Z is R10CN;
• R10 is hydrocarbyl not containing olefinic or acetylenic bonds;
• R15 is hydrocarbyl not containing olefinic or acetylenic bonds;
• R2 and R5 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
• R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring.

A compound of the formula

• 127
• wherein:
• R2 and R5 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;
• R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
• each R27 is hydrocarbyl;
• and
• each X is a weakly coordinating anion.

A compound of the formula

• 128
• wherein:
• M is Ni(II) or Pd(II);
• R2 and R5 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;
• R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
• each R14 is independently hydrogen, alkyl or —(CH2)mCO2R1;
• R1 is hydrogen, or hydrocarbyl or substituted hydrocarbyl containing 1 to 10 carbon atoms;
• T4 is alkyl, —R60C(O)OR8, R15(C═O)— or R15OC(═O)—;
• R15 is hydrocarbyl not containing olefinic or acetylenic bonds;
• R60 is alkylene not containing olefinic or acetylenic bonds;
• 8 is as hydrocarbyl;
• and X is a weakly coordinating anion;
• and provided that when R14is —(CH2)mCO2R1, or T4 is not alkyl, M is Pd(II).

A polymerization process, comprising, contacting an olefin of the formula R17CH═CH2 or R17CH═CHR17, each R17 is independently hydrogen, hydrocarbyl, or substituted hydrocarbyl provided any olefinic bond in said olefin is separated f other olefinic bond or aromatic ring by a quate:

• 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−1s−1 when said catalyst contains a palladium atom, and less than 50,000 L-mol−1s−1 when said catalyst contains a nickel atom;
• and provided that when M is Pd a diene is not present.

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 source of a relatively noncoordinating monoanion;
• a second compound of the formula
• 129
• and one or more monomers selected from the group consisting of ethylene, an olefin of the formula R17CH═CH2 or R17CH═CHR17, cyclobutene, cyclopentene, substituted norbornene, or norbornene;
• wherein:
• R2 and R5 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;
• R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
• each R17 is independently hydrocarbyl or substituted hydrocarbyl provided that R17 does not contain any olefinic bonds;
• T1 is hydrogen, hydrocarbyl not containing olefinic or acetylenic bonds, R15C(═O)— or R15OC(═O)—;
• S is chloride, iodide, or bromide;
• and
• provided that, when norbornene or substituted norbornene is present, no_other monomer is present.

A polyolefin, comprising, a polymer made by polymerizing one or more monomers of the formula H2C═CH(CH2)eG by contacting said monomers with a transition metal containing coordination polymerization catalyst, wherein:

• each G is independently hydrogen or —CO2R1;
• each e is independently 0 or an integer of 1 to 20;
• each R1 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;
• 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.

A polyolefin, comprising, a polymer made by polymerizing one or more monomers of the formula H2C═CH(CH2)eG by contacting said monomers with a transition metal containing coordination polymerization catalyst, wherein:

• each G is independently hydrogen or —CO2R1;
• each e is independently 0 or an integer of 1 to 20;
• R1 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;
• said polymer has at least 50 branches of the formula —(CH2)fG 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 H2C═CH(CH2)eG 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 —(CH2)fG 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 each.

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
• 134
• wherein:
• R2 and R5 are each independently hydrocarbyl or substituted hydrocarbyl;
• R3 and R4 are each independently hydrogen, substituted hydrocarbyl, hydrocarbyl, or R3 and R4 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.

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
• 135
• wherein:
• R2 and R5 are each independently hydrocarbyl or substituted hydrocarbyl;
• R3 and R4 are each independently hydrogen, substituted hydrocarbyl, hydrocarbyl, or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
• T1 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.

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

• 136
• and one or more monomers selected from the group consisting of ethylene, an olefin of the formula R17CH═CH2 or R17CH═CHR17, cyclobutene, cyclopentene, substituted norbornene, and norbornene,
• wherein:
• M is Ni(II) or Pd(II);
• A is a π-allyl or π-benzyl group;
• R2 and R5 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;
• R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
• each R17 is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said olefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms;
• R1 is hydrogen, or hydrocarbyl or substituted hydrocarbyl containing 1 to 10 carbon atoms;
• and X is a weakly coordinating anion;
• and provided that;
• when norbornene or substituted norbornene is present, no other monomer is present;
• and
• when M is Pd a diene is not present.

A compound of the formula

• 138
• wherein:
• M is Ni(II) or Pd(II);
• A is a π-allyl or 90 -benzyl group;
• R2 and R5 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;
• R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
• each R17 is independently hydrocarbyl or substituted hydrocarbyl provided that any olefinic bond in said olefin is separated from any other olefinic bond or aromatic ring by a quaternary carbon atom or at least two saturated carbon atoms;
• R1 is hydrogen, or hydrocarbyl or substituted hydrocarbyl containing 1 to 10 carbon atoms;
• and X is a weakly coordinating anion;
• and provided that when M is Pd a diene is not present.

A compound of the formula

• 140
• wherein:
• R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
• R54 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 R55 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 olefin of the formula R17CH═CHR17;
• each R17 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 R17 is independently hydrogen or saturated hydrocarbyl.

A process for the production of a compound of the formula

• 141
• comprising, heating a compound of the formula
• 142
• at a temperature of about −30° C. to about +100° for a sufficient time to produce (XXXVIII), and wherein:
• R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
• R54 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 R55 is independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or a functional group;
• R56 is alkyl containing 2 to 30 carbon atoms;
• T5 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.

A process for the polymerization of olefins, comprising, contacting a compound of the formula

• 143
• and one or more monomers selected from the group consisting of ethylene, an olefin of the formula R17CH═CH2 or R17CH═CHR17, cyclobutene, cyclopentene, substituted norbornene, and norbornene,
• wherein:
• R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a ring;
• R54 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 R55 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 olefin of the formula R17CH═CHR17;
• each R17 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 R17 is independently hydrogen or saturated hydrocarbyl;
• and when norbornene or substituted norbornene is present, no other monomer is present. 483. The process as recited in claim 482 wherein R3 and R4 are each independently hydrogen or hydrocarbyl, or R3 and R4 taken together are hydrocarbylene to form a ring;
• and R54 is hydrocarbyl.

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
• 144
• R2 and R5 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;
• R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R3 and R4 taken together are hydrocarbylene or substituted hydrocarbylene to form a carbocyclic ring and
• wherein an α-olefin containing 4 to 40 carbon atoms is produced.

A process, comprising, contacting, at a temperature of about −80° C. to about +20° C., a compound of the formula (η4-1,5-COD)PdMe2 and a diimine of the formula

• 145
• to produce a compound of the formula
• 146
• wherein:
• COD is 1,5-cyclooctadiene;
• R2 and R5 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
• R3 and R4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or R3 and R4taken together are hydrocarbylene or substituted hydrocarbylene to form a ring.