Substituted pyridyl amine catalysts and processes for polymerizing crystalline polymers

Abstract

New ligands, compositions, metal-ligand complexes and arrays with pyridyl-amine ligands are disclosed that catalyze the polymerization of monomers into polymers. Certain of these catalysts with hafnium metal centers have high performance characteristics, including higher comonomer incorporation into ethylene/olefin copolymers, where such olefins are for example, 1-octene, isobutylene or styrene. Certain of the catalysts are particularly effective at polymerizing propylene to high molecular weight isotactic polypropylene in a solution process at a variety of polymerization conditions.

1 . Isotactic polypropylene produced by polymerization of propylene with the aid of a catalyst that comprises Hf or Zr in a solution polymerization process, wherein the tacticity index value of the polypropylene does not vary by more than 0.1 when the temperature of the solution process is varied from a temperature below 90° C. to a temperature above 100° C.  
     
     
         2 . Isotactic polypropylene produced by polymerization of propylene with the with the aid of a catalyst that comprises Hf or Zr in a solution polymerization process, wherein the melting point of the polypropylene does not vary by more than 10° C. when the temperature of the solution process is varied from a temperature below 90° C. to a temperature above 100° C.  
     
     
         3 . Isotactic polypropylene produced by polymerization of propylene with the with the aid of a catalyst that comprises Hf or Zr in a solution polymerization process, wherein the temperature of the solution process is at least 110° C. and the polypropylene has a weight average molecular weight of at least 100,000.  
     
     
         4 . The isotactic polypropylene of either of claims  1  or  2 , wherein said solution process is operated at a temperature at or above 110° C.  
     
     
         5 . The isotactic polypropylene of either of claims  1 ,  2 , or  3 , wherein said catalyst is formed from a composition comprising: 
 (1) a ligand characterized by the following general formula:                          wherein R 1  is characterized by the general formula:                          wherein E is either carbon or nitrogen,    Q 1  and Q 5  are substituents on the R 1  ring at a position ortho to E, with Q 1  and Q 5  are independently selected from the group consisting of alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, aryl, substituted aryl and silyl, but provided that Q 1  and Q 5  are not both methyl;    Q″ q  represents additional possible substituents on the ring, with q being 1, 2, 3, 4 or 5 and Q″ being selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl, silyl, boryl, phosphino, amino, thio, seleno, halide, nitro, and combinations thereof;    T is a bridging group selected group consisting of —CR 2 R 3 — and —SiR 2 R 3 — with R 2  selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl, silyl, boryl, phosphino, amino, thio, seleno, halide, nitro, and combinations thereof; R 3  selected from the group consisting of aryl, substituted aryl, heteroaryl, and substituted heteroaryl; and provided that R 2  is different from R 3 ;    J″ is selected from the group consisting of heteroaryl and substituted heteroaryl;    (2) a metal precursor compound characterized by the general formula M(L) n  wherein M is either hafnium or zirconium and each L is independently selected from the group consisting of halide, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, hydroxy, boryl, silyl, amino, amine, hydrido, allyl, diene, seleno, phosphino, phosphine, carboxylates, thio, 1,3-dionates, oxalates, carbonates, nitrates, sulphates, ethers, thioethers and combinations thereof or optionally two or more L groups are joined into a ring structure; n is 1, 2, 3, 4, 5, or 6; and    (3) optionally, at least one activator.    
     
     
         6 . The isotactic polypropylene of either of claims  1 ,  2 , or  3 , wherein said catalyst is formed from a composition comprising: 
 (1) a ligand characterized by the formula:                          wherein each of R 4 , R 5 , R 6  and R 7  is independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl, silyl, boryl, phosphino, amino, thio, seleno, halide, nitro, and combinations thereof; and optionally, any combination of R 1 , R 2 , R 3 , R 4 , R 5 , R 6  or R 7  may be joined together in a ring structure;    (2) a metal precursor compound characterized by the general formula M(L) n  wherein M is either hafnium or zirconium and each L is independently selected from the group consisting of halide, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, hydroxy, boryl, silyl, amino, amine, hydrido, allyl, diene, seleno, phosphino, phosphine, carboxylates, thio, 1,3-dionates, oxalates, carbonates, nitrates, sulphates; ethers, thioethers and combinations thereof or optionally two or more L groups are joined into a ring structure; n is 1, 2, 3, 4, 5, or 6; and    (3) optionally, at least one activator.    
     
     
         7 . The isotactic polypropylene of either of claims  1 ,  2 , or  3 , wherein said catalyst is formed from a composition of comprising: 
 (1) a ligand characterized by the general formula:                          such that E is carbon and wherein Q 2 , Q 3  and Q 4  are independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl, silyl, boryl, phosphino, amino, thio, seleno, nitro, and combinations thereof, optionally two or more of Q 2 , Q 3  and Q 4  are joined together in a ring structure;    (2) a metal precursor compound characterized by the general formula M(L) n  wherein M is either hafnium or zirconium and each L is independently selected from the group consisting of halide, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, hydroxy, boryl, silyl, amino, amine, hydrido, allyl, diene, seleno, phosphino, phosphine, carboxylates, thio, 1,3-dionates, oxalates, carbonates, nitrates, sulphates, ethers, thioethers and combinations thereof or optionally two or more L groups are joined into a ring structure; n is 1, 2, 3, 4, 5, or 6; and    (3) optionally, at least one activator.    
     
     
         8 . The isotactic polypropylene of either of claims  1 ,  2 , or  3 , wherein said catalyst is formed from a composition comprising: 
 (1) a ligand characterized by the general formula:                          such that T is —CR 2 R 3 — and wherein R 10 , R 11 , R 12  and R 13  are each independently selected from the group consisting of hydrogen, halide, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio, seleno, nitro, and combinations thereof; optionally, two or more R 10 , R 11 , R 12  and R 13  groups may be joined to form a fused ring system having from 3-50 non-hydrogen atoms; and R 14  is selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio, seleno, halide, nitro, and combinations thereof;    (2) a metal precursor compound characterized by the general formula M(L) n  wherein M is either hafnium or zirconium and each L is independently selected from the group consisting of halide, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, hydroxy, boryl, silyl, amino, amine, hydrido, allyl, diene, seleno, phosphino, phosphine, carboxylates, thio, 1,3-dionates, oxalates, carbonates, nitrates, sulphates, ethers, thioethers and combinations thereof or optionally two or more L groups are joined into a ring structure; n is 1, 2, 3, 4, 5, or 6; and    (3) optionally, at least one activator.    
     
     
         9 . The isotactic polypropylene of either of claims  1 ,  2 , or  3 , wherein said catalyst is formed from a composition comprising: 
 (1) a ligand of the formula                          such that E is carbon and wherein Q 2 , Q 3  and Q 4  are independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl, silyl, boryl, phosphino, amino, thio, seleno, nitro, and combinations thereof; optionally two or more of Q 2 , Q 3  and Q 4  are joined together in a ring structure;    (2) a metal precursor compound characterized by the general formula M(L) n  wherein M is either hafnium or zirconium and each L is independently selected from the group consisting of halide, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, hydroxy, boryl, silyl, amino, amine, hydrido, allyl, diene, seleno, phosphino, phosphine, carboxylates, thio, 1,3-dionates, oxalates, carbonates, nitrates, sulphates, ethers, thioethers and combinations thereof or optionally two or more L groups are joined into a ring structure; n is 1, 2, 3, 4, 5, or 6; and    (3) optionally, at least one activator.    
     
     
         10 . The isotactic polypropylene of either of claims  1 ,  2 , or  3 , wherein said catalyst comprises hafnium.  
     
     
         11 . The isotactic polypropylene of either of claims  1 ,  2 , or  3 , wherein said catalyst is formed from a composition comprising: 
 (1) a metal-ligand complex characterized by the following formula:                          wherein R 1  is characterized by the general formula:                          wherein E is either carbon or nitrogen;    Q 1  and Q 5  are substituents on the R 1  ring at a position ortho to E, with Q 1  and Q 5  being independently selected from the group consisting of alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, aryl, substituted aryl and silyl, but provided that Q 1  and Q 5  are not both methyl;    Q″ q  represents additional possible substituents on the ring, with q being 1, 2, 3, 4 or 5 and Q″ being selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl, silyl, boryl, phosphino, amino, thio, seleno, halide, nitro, and combinations thereof;    T is a bridging group selected group consisting of —CR 2 R 3 — and —SiR 2 R 3 — with R 2  selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl, silyl, boryl, phosphino, amino, thio, seleno, halide, nitro, and combinations thereof; R 3  selected from the group consisting of aryl, substituted aryl, heteroaryl, and substituted heteroaryl; and provided that R 2  is different from R 3 ;    J″ is selected from the group consisting of heteroaryl and substituted heteroaryl;    each L is independently selected from the group consisting of halide, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, hydroxy, boryl, silyl, amino, amine, hydrido, allyl, diene, seleno, phosphino, phosphine, carboxylates, thio, 1,3-dionates, oxalates, carbonates, nitrates, sulphates, ethers, thioethers and combinations thereof or optionally two or more L groups are joined into a ring structure; n is 1, 2, 3, 4, 5, or 6; and x is 1;    (2) a metal precursor compound characterized by the general formula M(L) n  wherein M is either hafnium or zirconium and each L is independently selected from the group consisting of halide, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, hydroxy, boryl, silyl, amino, amine, hydrido, allyl, diene, seleno, phosphino, phosphine, carboxylates, thio, 1,3-dionates, oxalates, carbonates, nitrates, sulphates, ethers, thioethers and combinations thereof or optionally two or more L groups are joined into a ring structure; n is 1, 2, 3, 4, 5, or 6; and    (3) optionally, at least one activator.    
     
     
         12 . The isotactic polypropylene of either of claims  1 ,  2 , or  3 , wherein said catalyst is formed from a composition comprising: 
 (1) a metal complex having the formula:                          wherein each of R 4 , R 5 , R 6  and R 7  is independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl, silyl, boryl, phosphino, amino, thio, seleno, halide, nitro, and combinations thereof, and optionally, any combination of R 1 , R 2 , R 3 , R 4 , R 5 , R 6  or R 7  may be joined together in a ring structure;    (2) a metal precursor compound characterized by the general formula M(L) n  wherein M is either hafnium or zirconium and each L is independently selected from the group consisting of halide, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, hydroxy, boryl, silyl, amino, amine, hydrido, allyl, diene, seleno, phosphino, phosphine, carboxylates, thio, 1,3-dionates, oxalates, carbonates, nitrates, sulphates, ethers, thioethers and combinations thereof or optionally two or more L groups are joined into a ring structure; n is 1, 2, 3, 4, 5, or 6; and    (3) optionally, at least one activator.    
     
     
         13 . The isotactic polypropylene of either of claims  1 ,  2 , or  3 , wherein said catalyst is formed from a composition comprising: 
 (1) a metal complex having the formula:                          such that E is carbon and wherein Q 2 , Q 3  and Q 4  are independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl, silyl, boryl, phosphino, amino, thio, seleno, nitro, and combinations thereof; optionally two or more of Q 2 , Q 3  and Q 4  are joined together in a ring structure;    (2) a metal precursor compound characterized by the general formula M(L) n  wherein M is either hafnium or zirconium and each L is independently selected from the group consisting of halide, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, hydroxy, boryl, silyl, amino, amine, hydrido, allyl, diene, seleno, phosphino, phosphine, carboxylates, thio, 1,3-dionates, oxalates, carbonates, nitrates, sulphates, ethers, thioethers and combinations thereof or optionally two or more L groups are joined into a ring structure; n is 1, 2, 3, 4, 5, or 6; and    (3) optionally, at least one activator.    
     
     
         14 . The isotactic polypropylene of either of claims  1 ,  2 , or  3 , wherein said catalyst is formed from a composition comprising: 
 (1) a metal complex, wherein said complex is characterized by the formula:                          such that T is —CR 2 R 3 — and wherein R 10 , R 11 , R 12  and R 13  are each independently selected from the group consisting of hydrogen, halide, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio, seleno, nitro, and combinations thereof; optionally, two or more R 10 , R 11 , R 12  and R 13  groups may be joined to form a fused ring system having from 3-50 non-hydrogen atoms; and    R 14  is selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio, seleno, halide, nitro, and combinations thereof;    (2) a metal precursor compound characterized by the general formula M(L) n  wherein M is either hafnium or zirconium and each L is independently selected from the group consisting of halide, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, hydroxy, boryl, silyl, amino, amine, hydrido, allyl, diene, seleno, phosphino, phosphine, carboxylates, thio, 1,3-dionates, oxalates, carbonates, nitrates, sulphates, ethers, thioethers and combinations thereof or optionally two or more L groups are joined into a ring structure; n is 1, 2, 3, 4, 5, or 6; and    (3) optionally, at least one activator.    
     
     
         15 . The isotactic polypropylene of either of claims  1 ,  2 , or  3 , wherein said catalyst is formed from a composition comprising: 
 (1) a metal complex, wherein said complex is characterized by the general formula:                          such that E is carbon and wherein Q 2 Q 3  and Q 4  are independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl, silyl, boryl, phosphino, amino, thio, seleno, nitro, and combinations thereof; optionally two or more of Q 2 , Q 3  and Q 4  are joined together in a ring structure;    (2) a metal precursor compound characterized by the general formula M(L) n  wherein M is either hafnium or zirconium and each L is independently selected from the group consisting of halide, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, hydroxy, boryl, silyl, amino, amine, hydrido, allyl, diene, seleno, phosphino, phosphine, carboxylates, thio, 1,3-dionates, oxalates, carbonates, nitrates, sulphates, ethers, thioethers and combinations thereof or optionally two or more L groups are joined into a ring structure; n is 1, 2, 3, 4, 5, or 6; and    (3) optionally, at least one activator.    
     
     
         16 . The isotactic polypropylene of either of claims  1 ,  2 , or  3 , wherein said catalyst is formed from a composition comprising: 
 (1) a metal complex characterized by the formula:                          where M is zirconium or hafnium;    wherein R 1  is characterized by the general formula:                          wherein E is either carbon or nitrogen,    Q 1  and Q 5  are substituents on the R 1  ring at a position ortho to E, with Q 1  and Q 5  are independently selected from the group consisting of alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, aryl, substituted aryl and silyl, but provided that Q 1  and Q 5  are not both methyl;    Q″ q  represents additional possible substituents on the ring, with q being 1, 2, 3, 4 or 5 and Q″ being selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl, silyl, boryl, phosphino, amino, thio, seleno, halide, nitro, and combinations thereof,    T is a bridging group selected group consisting of —CR 2 R 3 — and —SiR 2 R 3 — with R 2  selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl, silyl, boryl, phosphino, amino, thio, seleno, halide, nitro, and combinations thereof; R 3  selected from the group consisting of aryl, substituted aryl, heteroaryl, and substituted heteroaryl; and provided that R 2  is different from R 3 ;    J′″ being selected from the group of substituted heteroaryls with 2 atoms bonded to the metal M, at least one of those 2 atoms being a heteroatom, and with one atom of J′″ is bonded to M via a dative bond, the other through a covalent bond; and    L 1  and L 2  are independently selected from the group consisting of halide, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, hydroxy, boryl, silyl, amino, amine, hydrido, allyl, diene, seleno, phosphino, phosphine, carboxylates, thio, 1,3-dionates, oxalates, carbonates, nitrates, sulphates, ethers, thioethers and combinations thereof or optionally the two L groups are joined into a ring structure;    (2) a metal precursor compound characterized by the general formula M(L) n  wherein M is either hafnium or zirconium and each L is independently selected from the group consisting of halide, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, hydroxy, boryl, silyl, amino, amine, hydrido, allyl, diene, seleno, phosphino, phosphine, carboxylates, thio, 1,3-dionates, oxalates, carbonates, nitrates, sulphates, ethers, thioethers and combinations thereof or optionally two or more L groups are joined into a ring structure; n is 1, 2, 3, 4, 5, or 6; and    (3) optionally, at least one activator.    
     
     
         17 . The isotactic polypropylene of either of claims  1 ,  2 , or  3 , wherein said catalyst is formed from a composition comprising: 
 (1) a metal complex characterized by the formula:                          wherein each of R 4 , R 5  and R 6  is independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl, silyl, boryl, phosphino, amino, thio, seleno, halide, nitro, and combinations thereof; and optionally, any combination of R 1 , R 2 , R 3 , R 4 , R 5 , or R 6  may be joined together in a ring structure; and    E″ is either carbon or nitrogen and is part of a cyclic aryl, substituted aryl, heteroaryl, or substituted heteroaryl group;    (2) a metal precursor compound characterized by the general formula M(L) n  wherein M is either hafnium or zirconium and each L is independently selected from the group consisting of halide, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, hydroxy, boryl, silyl, amino, amine, hydrido, allyl, diene, seleno, phosphino, phosphine, carboxylates, thio, 1,3-dionates, oxalates, carbonates, nitrates, sulphates, ethers, thioethers and combinations thereof or optionally two or more L groups are joined into a ring structure; n is 1, 2, 3, 4, 5, or 6; and    (3) optionally, at least one activator.    
     
     
         18 . The isotactic polypropylene of either of claims  1 ,  2 , or  3 , wherein said catalyst is formed from a composition comprising: 
 (1) a metal complex, wherein said complex is characterized by the formula:                          wherein R 10 , R 11 , R 12  and R 13  are each independently selected from the group consisting of hydrogen, halide, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio, seleno, nitro, and combinations thereof; optionally, two or more R 10 , R 11 , R 12  and R 13  groups may be joined to form a fused ring system having from 3-50 non-hydrogen atoms;    (2) a metal precursor compound characterized by the general formula M(L) n  wherein M is either hafnium or zirconium and each L is independently selected from the group consisting of halide, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, hydroxy, boryl, silyl, amino, amine, hydrido, allyl, diene, seleno, phosphino, phosphine, carboxylates, thio, 1,3-dionates, oxalates, carbonates, nitrates, sulphates, ethers, thioethers and combinations thereof or optionally two or more L groups are joined into a ring structure; n is 1, 2, 3, 4, 5, or 6; and    (3) optionally, at least one activator.    
     
     
         19 . The isotactic polypropylene of either of claims  1 ,  2 , or  3 , wherein said catalyst is formed from a composition comprising: 
 (1) a metal complex, wherein said complex is characterized by the formula:                          wherein Q 2 , Q 3  and Q 4  are independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted hetercycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxyl, aryloxyl, silyl, boryl, phosphino, amino, thio, seleno, nitro, and combinations thereof; or optionally, two of Q 2 , Q 3  and Q 4  are joined together in a ring structure;    (2) a metal precursor compound characterized by the general formula M(L) n  wherein M is either hafnium or zirconium and each L is independently selected from the group consisting of halide, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, hydroxy, boryl, silyl, amino, amine, hydrido, allyl, diene, seleno, phosphino, phosphine, carboxylates, thio, 1,3-dionates, oxalates, carbonates, nitrates, sulphates, ethers, thioethers and combinations thereof or optionally two or more L groups are joined into a ring structure; n is 1, 2, 3, 4, 5, or 6; and    (3) optionally, at least one activator.