Phenol-heterocyclic ligands, metal complexes, and their uses as catalysts

Abstract

Ligands, compositions, and metal-ligand complexes that incorporate phenol-heterocyclic compounds are disclosed that are useful in the catalysis of transformations such as the polymerization of monomers into polymers. The catalysts have high performance characteristics, including high comonomer incorporation into ethylene/olefin copolymers, where such olefins are for example, 1-octene, propylene or styrene. The catalysts particularly polymerize styrene to form polystyrene.

1 . A catalyst comprising (a) a metal ligand complex characterized by the general formula: 
     
       
         
         
             
             
         
       
       wherein each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7  are the same or different and are independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, halo, silyl, boryl, phosphino, amino, thioalkyl, thioaryl, nitro, and combinations thereof, with the exception that R 1  may not be hydrogen, optionally two or more of R 1 , R 2 , R 3  and R 4  may be joined to form a fused ring system having up to 50 atoms, not counting hydrogen atoms, and optionally two or more of R 5 , R 6  and R 7  may be joined to form a fused ring system having up to 50 atoms, not counting hydrogen atoms; 
       X 1  is N or C, X 2  is O, S, N(R 5 ) n′  or CR 5 , X 3  is O, S, N(R 6 ) n″  or CR 6 , X 4  is O, S, N(R 7 ) n′″  or CR 7 , wherein each n′, n″, and n′″ are each independently 0 or 1, provided that the heteroatom containing ring system is heteroaromatic; 
       provided combinations of X 1 , X 2 ; X 1 , X 3 ; and X 1 , X 4  are not both N and X 1 , X 2  and X 3  are not all N; further provided where X 1 , X 3 , X 4  are each N, X 2  is C, R 5  is H and R 1  is selected from the group consisting of t-butyl, —CMe 2 Et, —C(Et) 3 , —CMe 2 Ph, —C(Ph) 3 , —Si(Et) 3 , and —Si(Ph) 3 , and when R 1  is F, R 3  is F, X 1 , X 2 , X 3  are all C, X 4  is N, R 5 , R 6  are each H and R 7  is t-butyl are not included; 
       wherein M is a metal selected from the group consisting of groups 3 through 6 of the periodic table elements and lanthanides; 
       wherein each L is independently selected from the group consisting of hydrogen, halogen, optionally substituted alkyl, heteroalkyl, allyl, diene, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, aryl, heteroaryl, alkoxy, aryloxy, boryl, silyl, amino, phosphino, ether, thioether, phosphine, amine, carboxylate, alkylthio, arylthio, 1,3-dionate, oxalate, carbonate, nitrate, sulphate, and combinations thereof; 
       x is 1,2, 3, or 4; and 
       m″ is 0, 1, 2, 3, or 4; and, 
       (b) an activator, or a combination of activators. 
     
   
   
       2 . The catalyst of  claim 1 , wherein the metal ligand complex is characterized by a formula selected from the group consisting of: 
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
   
   
       3 . The catalyst of  claim 2 , wherein R 1  and R 7  are independently selected from the group consisting of optionally substituted alkyl, heteroalkyl, aryl and heteroaryl. 
   
   
       4 . The catalyst of  claim 3 , wherein R 1  is selected from the group consisting of t-butyl, naphthyl, substituted naphthyl, N-carbazolyl, substituted N-carbazolyl, phenyl and substituted phenyl and R 7  is selected from the group consisting of substituted phenyl and anthracenyl. 
   
   
       5 . The catalyst of  claim 2 , wherein x is 2 forming a bis-ligand complex and wherein each of the two ligands within the square brackets is identical to the other. 
   
   
       6 . The catalyst of  claim 2 , wherein the catalyst is supported. 
   
   
       7 . The catalyst of  claim 1 , wherein R1 and R7 are independently selected from the group consisting of optionally substituted alkyl, heteroalkyl, aryl and heteroaryl. 
   
   
       8 . The catalyst of  claim 1 , wherein x is 2 forming a bis-ligand complex and wherein each of the two ligands within the square brackets is identical to the other. 
   
   
       9 . The catalyst of  claim 1 , wherein x is 2 forming a bis-ligand complex comprising a first phenol-heterocycle ligand. 
   
   
       10 . The catalyst of  claim 1 , wherein the catalyst is supported. 
   
   
       11 . A catalyst comprising (a) a composition comprising:
 (i) a compound characterized by the general formula:   
     
       
         
         
             
             
         
       
       wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7  are independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, halo, silyl, boryl, phosphino, amino, thioalkyl, thioaryl, nitro, and combinations thereof, with the exception that R 1  may not be hydrogen, optionally two or more of R 1 , R 2 , R 3  and R 4  may be joined to form a fused ring system having up to 50 atoms, not counting hydrogen atoms, and optionally two or more of R 5 , R 6  and R 7  may be joined to form a fused ring system having up to 50 atoms, not counting hydrogen atoms; 
       X1 is N or C, X2 is O, S, N(R5)n′ or CR5, X3 is O, S, N(R6)n″ or CR6, X4 is O, S, N(R7)n′″ or CR7, wherein each n′, n″, and n′″ are each independently 0 or 1, provided that the heteroatom containing ring system is heteroaromatic; 
       provided combinations of X1, X2; X1, X3; and X1, X4 are not both N and X1, X 2  and X3 are not all N; and 
       further provided compounds where X1, X3, X4 are each N, X2 is C, R 5  is H and R1 is selected from the group consisting of t-butyl, —CMe2Et, —C(Et)3, —CMe2Ph, —C(Ph)3, —Si(Et)3, and —Si(Ph)3; and when R1 is F, R3 is F, X1, X2, X3 are all C, X4 is N, R5, R6 are each H and R7 is t-butyl are not included; and 
       (ii) a metal precursor characterized by the general formula M(L)n, where M is a metal selected from groups 3-6 of the periodic table of elements and lanthanide elements of the periodic table of elements, each L is a moiety that forms a covalent, dative or ionic bond with M, and n is 1, 2, 3, 4, 5, or 6; and, 
       (b) an activator, or a combination of activators. 
     
   
   
       12 . The catalyst of  claim 11 , wherein the compound in part (i) is characterized by a formula selected from the group consisting of: 
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
   
   
       13 . The catalyst of  claim 12 , wherein the ratio of the compound of part (i) to the metal precursor is about two equivalents to one equivalent, and wherein the about two compound equivalents are the same. 
   
   
       14 . The catalyst of  claim 12 , wherein the catalyst is supported. 
   
   
       15 . The catalyst of  claim 11 , wherein R1 and R7 are independent selected from the group consisting of optionally substituted alkyl, heteroalkyl, aryl, and heteroaryl. 
   
   
       16 . The catalyst of  claim 11 , wherein RI is selected from the group consisting of t-butyl, naphthyl, substituted naphthyl, carbazolyl, substituted carbazolyl, phenyl and substituted phenyl and R7 is selected from the group consisting of substituted phenyl and anthracenyl. 
   
   
       17 . The catalyst of  claim 11 , wherein the ratio of the compound of part (i) to the metal precursor is about two equivalents to one equivalent, and wherein the about two compound equivalents are the same. 
   
   
       18 . The catalyst of  claim 11 , wherein each L is independently selected from the group consisting of hydrogen, halogen, optionally substituted alkyl, heteroalkyl, allyl, diene, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, aryl, heteroaryl, alkoxy, aryloxy, boryl, silyl, amino, phosphino, ether, thioether, phosphine, amine, carboxylate, alkylthio, arylthio, 1,3-dionate, oxalate, carbonate, nitrate, sulphate, and combinations thereof, and Lewis base adducts thereof. 
   
   
       19 . The catalyst of  claim 11 , wherein the catalyst is supported. 
   
   
       20 . A polymerization process comprising subjecting one or more monomers to polymerization conditions in the presence of a catalyst comprising (a) a metal ligand complex characterized by the general formula: 
     
       
         
         
             
             
         
       
       wherein each R1, R2, R3, R4, R5, R6, and R7 are the same or different and are independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, halo, silyl, boryl, phosphino, amino, thioalkyl, thioaryl, nitro, and combinations thereof, with the exception that R1 may not be hydrogen, optionally two or more of R1, R2, R3 and R4 may be joined to form a fused ring system having up to 50 atoms, not counting hydrogen atoms, and optionally two or more of R5, R6 and R7 may be joined to form a fused ring system having up to 50 atoms, not counting hydrogen atoms; 
       X1 is N or C, X2 is O, S, N(R5)n′ or CR5, X3 is O, S, N(R6)n″ or CR6, X4 is O, S, N(R7)n′″ or CR7, wherein each n′, n″, and n′″ are each independently 0 or 1, provided that the heteroatom containing ring system is heteroaromatic; 
       provided combinations of X1, X2; X1, X3; and X1, X4 are not both N and X1, X2 and X3 are not all N; 
       further provided where X1, X3, X4 are each N, X2 is C, R5 is H and R1 is selected from the group consisting of t-butyl, —CMe2Et, —C(Et)3, —CMe2Ph, —C(Ph)3, —Si(Et)3, and —Si(Ph)3, and when R1 is F, R3 is F, X1, X2, X3 are all C, X4 is N, R5, R6 are each H and R7 is t-butyl are not included; 
       wherein M is a metal selected from the group consisting of groups 3 through 6 of the periodic table elements and lanthanides; 
       wherein each L is independently selected from the group consisting of hydrogen, halogen, optionally substituted alkyl, heteroalkyl, allyl, diene, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, aryl, heteroaryl, alkoxy, aryloxy, boryl, silyl, amino, phosphino, ether, thioether, phosphine, amine, carboxylate, alkylthio, arylthio, 1,3-dionate, oxalate, carbonate, nitrate, sulphate, and combinations thereof; 
       x is 1, 2, 3, or 4; and 
       m″ is 0, 1, 2, 3, or 4; and, 
       (b) an activator, or a combination of activators. 
     
   
   
       21 . The process of  claim 20 , wherein the metal ligand complex is characterized by a formula selected from the group consisting of: 
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
   
   
       22 . The process of  claim 21 , wherein R1 and R7 are independently selected from the group consisting of optionally substituted alkyl, heteroalkyl, aryl and heteroaryl. 
   
   
       23 . The process of  claim 22 , wherein RI is selected from the group consisting of t-butyl, naphthyl, substituted naphthyl, N-carbazolyl, substituted N-carbazolyl, phenyl and substituted phenyl and R7 is selected from the group consisting of substituted phenyl and anthracenyl. 
   
   
       24 . The process of  claim 22 , wherein x is 2 forming a bis-ligand complex and wherein each of the two ligands within the square brackets is identical to the other. 
   
   
       25 . The process of  claim 22 , wherein the catalyst is supported.