Catalyst ligands, catalytic metal complexes and processes using same

Abstract

A new ligands that include a benzene ring in the backbone can be combined with a metal or metal precursor compound or formed into a metal-ligand complex catalyze a number of different chemical transformations, including olefin polymerization reactions. The ligands, complexes formed with the ligands and compositions including the ligands are useful catalysts, depending on the reaction.

1 - 108  canceled.  
     
     
         109 . A complex characterized by one of the following general formulas:  
       
         
           
           
               
               
           
         
         wherein each R′, R 2 , R 3 , R 4  R 5  and R 6  is independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio, seleno, and combinations thereof optionally, R′ and R 2  are joined together in a ring structure and/or R 4  and R 5  are joined together in a ring structure;  
         G is either nitrogen or oxygen and a is 1 or 2 depending on G;  
         B is 0, 1, 2, 3 or 4;  
         M is a transition metal selected from the group consisting of Groups 3, 4, 5, 6, 7, 8, 9 and 10 of the Periodic Table of Elements;  
         L is independently each occurrence, a ligand;  
         n is a number 0, 1, 2, 3,4, and 5; and  
         m is 1, 2, 3 or 4.  
       
     
     
         110 . The complex of  claim 109 , wherein M is selected from the group consisting of Sc, Y, Zr, Ti, H1 V, Nb, Ta, Cr, Mo, Mn, Fe, Ru, Co, Rh, Ni, Pd, Pt.  
     
     
         111 . The complex of  claim 110 , wherein M is selected from the group consisting of Pd, Ni, Co, Fe, Ru, Rh, Ir, Pt, Cr, Mo, Mn, and V.  
     
     
         112 . The complex of  claim 109 , wherein L is selected from the group consisting of hydrogen, halogens, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio, seleno, and combinations thereof.  
     
     
         113 . The complex of  claim 109 , wherein L is selected from the group consisting ofcarbon monoxide, is 6cyanide, nitrous oxide, PA 3 , NA 3 , OA 2 , SA 2 , SeA 2 , and combinations thereof, wherein each A is independently selected from a group consisting ofalkyl, substituted alkyl, heteroalkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, and amino.  
     
     
         114 . The complex of  claim 109 , wherein R 1  is a substituted or unsubstitued phenyl.  
     
     
         115 . The complex of  claim 114 , wherein R 1  is a substituted phenyl and there are from 1-5 substituents on said phenyl ring, with each of said substituents independently selected from the group consisting of halogens, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio, seleno, and combinations thereof.  
     
     
         116 . The complex of  claim 115 , wherein there are 1, 2 or 3 substituents on said substituted phenyl and said substituents are selected from the group consisting of chloro, fluoro, iodo, bromo, methyl, ethyl, propyl, butyl, cyclopentyl, cylcohexyl, cyclooctyl, phenyl, naphthyl, benzyl, trimethylsilyl and isomers thereof.  
     
     
         117 . The complex of  claim 109 , wherein R 4  is selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, amino and silyl.  
     
     
         118 . The complex of  claim 117 , wherein R 4  is selected from the group consisting of hydrogen, alkyl, aryl and cycloalkyl.  
     
     
         119 . The complex of  claim 109 , wherein R 4  is joined in a ring structure with G and R 3 , wherein said ring has at least four atoms in the backbone of the ring.  
     
     
         120 . The complex of  claim 119 , wherein G is nitrogen and R 3  forms a methylene bridge to R 4 .  
     
     
         121 . The complex of  claim 109 , wherein G is nitrogen and a is 2 and each R 3  is independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio, seleno and combinations thereof.  
     
     
         122 . The complex of  claim 109 , wherein at least one R 3  is benzyl or a substituted or unsubstituted phenyl.  
     
     
         123 . The complex of  claim 122 , wherein said R 3  is a substituted phenyl and there are from 1-5 substituents on said phenyl ring, with each of said substituents independently selected from the group consisting of halogens, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio, seleno, and combinations thereof.  
     
     
         124 . The complex of  claim 123 , wherein there are 1, 2 or 3 substituents on said substituted phenyl and said substituents are selected from the group consisting of chloro, fluoro, iodo, bromo, methyl, ethyl, propyl, butyl, cyclopentyl, cylcohexyl, cyclooctyl, phenyl, naphthyl, benzyl, trimethylsilyl and isomers thereof.  
     
     
         125 . The complex of  claim 109 , wherein R 6  is selected from the group consisting of alkyl, aryl and cycloalkyl and b is 1, 2, 3 or 4.  
     
     
         126 . The complex of  claim 109 , wherein b is 2 and the two R. 6  groups are joined into a substituted or unsubstituted fused ring structure with the benzene ring in the backbone of the compound.  
     
     
         127 . The complex of  claim 109 , wherein G is oxygen and a is 1.  
     
     
         128 . The complex of  claim 109 , wherein R 1  and R 2  are joined in a ring, wherein the said ring has between 5 and 10 non-hydrogen atoms.  
     
     
         129 . The complex of  claim 129 , wherein said ring has between 5 and 6 non-hydrogen atoms in the backbone of the ring.  
     
     
         130 . The complex of  claim 109 , wherein each of R 1  and R 2  is independently selected from the group consisting of alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, aryl, substitute substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, amino and silyl.  
     
     
         131 . The complex of  claim 109 , wherein R 5  is selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, amino and silyl.  
     
     
         132 . The complex of  claim 131 , wherein R 5  is selected from the group consisting of hydrogen, alkyl, aryl and cycloalkyl.  
     
     
         133 . A composition of matter comprising a compound characterized by the general formula:  
       
         
           
           
               
               
           
         
         wherein each R 1  R 2  R 3 , R 4  R 5  and R 6  is independently selected from the group consisting of hydrogen alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy. silyl, boryl, phosphino, amino, thio, seleno, and combinations thereof, optionally, R 1  and R 2  are joined together in a ring structure and/or R 3  and R 4  are joined together in a ring structure and/or R 4  and R 5  are joined together in a ring structure and/or R 1  and R 6  are joined together in a ring structure;  
         G is either oxygen or nitrogen and a is either 1 or 2 depending on G, and b is 0, 1, 2, 3 or  4 , and  
         a metal precursor characterized by the general formula M(L) n , where M is a transition metal selected from the group consisting of Groups 3, 4, 5, 6, 7, 8, 9 and 10 of the Periodic Table of Elements; L is independently each occurrence, a ligand; and n is a number 0, 1, 2, 3, 4, and 5.  
       
     
     
         134 . The composition of  claim 133  wherein the ratio of compound to metal precursor is in the range of about 0.01:1 to about 100:1.  
     
     
         135 . The composition of  claim 134  wherein the ratio of compound to metal precursor is in the range of about 0.5:1 to about 20:1.  
     
     
         136 . The composition of  claim 133 , wherein R 1  is a substituted or unsubstitued phenyland R 2  is selected from the group consisting of alkyl substituted alkyl heteroalkyl, cycloalkyl, substituted cycloalkyl, aryl and substituted acryl.  
     
     
         137 . The composition of  claim 133 , wherein G is nitrogen and a is 2 and the two R 3  groups are independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio, seleno and combinations thereof.  
     
     
         138 - 145  canceled.  
     
     
         146 . A transition metal-catalyzed reaction employing complex in  claim 109 .  
     
     
         147 . The reaction of  claim 146 , wherein the reaction involves C—H, C—C, C—N, C—O, C—S, C—P, C-B and C-Si bond formation.  
     
     
         148 . The reaction of  claim 146 , wherein C—H, C—C, C—N, C—O, C—S, C—P, C-B, and C-Si bond formation involves a sp 2 -hybridized C atom.  
     
     
         149 . The reaction of  claim 146 , wherein the reactions involve carbonylation, hydroformylation, hydroxycarbonylation, hydrocarbonylation, hydroesterification, hydrogenation, hydrosilylation, hydroboration, hydroamination, epoxidation, aziridation, reductive amination, C—H activation, insertion, C—H activation-insertion, C—H activation-substitution, C-halogen activation, C-halogen activation-substitution, C-halogen activation-insertion, alkene metathesis, polymerization, alkene oligomerization, alkene polymerization, alkyne oligomerization, alkyne polymerization, co-polymerization, CO-alkene co-oligomerization, CO-alkene co-polymerization, CO-alkyne co-oligomerization, and CO-alkyne co-polymerization.  
     
     
         150 - 166  canceled.  
     
     
         167 . A process for polymerizing an olefin, diolefin or acetylenically unsaturated compound, comprising contacting said olefin, diolefin or acetylenically unsaturated compound to a complex that can be characterized by one of the following general formulas:  
       
         
           
           
               
               
           
         
         wherein each R 1 , R 2 , R 3 , R 4 , R 5  and R 6  is independently selected from the group consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio, seleno, and combinations thereof; optionally, R 1  and R 2  are joined together in a ring structure and/or R 4  and R 5  are joined together in a ring structure and/or R 4 6    and R 5  are joined together in a ring structure and/or R 1  and R 6  are joined together in a ring structure;  
         G is either nitrogen or oxygen and a is 1 or 2 depending on G;  
         b is 0, 1, 2, 3 or 4;  
         M is a transition metal selected from the group consisting of Groups 3, 4, 5, 6, 7, .8, 9 and 10 of the Periodic Table of Elements;  
         L is independently each occurrence, a ligand;  
         n is a number 0, 1, 2, 3, 4, and 5; and  
         mis 1, 2, 3 or 4.  
       
     
     
         168 . The process of  claim 167 , wherein M is selected from the group consisting of Sc, Y, Zr, Ti, Hf, V, Nb, Ta, Cr, Mo, Mn, Fe, Ru; Co, Rh, Ni, Pd, Pt.  
     
     
         169 . The process of  claim 168 , wherein M is selected from the group consisting of Pd, Ni, Co, Fe, Ru; Rh, Ir, Pt, Cr, Mo, Mn, and V.  
     
     
         170 . The process of  claim 167 , wherein L is selected from the group consisting of hydrogen, halogens, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio, seleno, and combinations thereof.  
     
     
         171 . The process of  claim 167 , wherein L is selected from the group consisting of carbon monoxide, isocyanide, nitrous oxide, PA 3 , NA 3 , OA 2 , SA 2 , SeA 2 , and combinations thereof wherein each A is independently selected from a group consisting of alkyl, substituted alkyl, heteroalkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, and amino.  
     
     
         172 . The process of  claim 167 , wherein R 1  is a substituted or unsubstitued phenyl.  
     
     
         173 . The process of  claim 172 , wherein R 1  is a substituted phenyl and there are from 1-5 substituents on said phenyl ring, with each of said substituents independently selected from the group consisting of alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heteroalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio, seleno, and combinations thereof.  
     
     
         174 . The process of  claim 167 , wherein said process is a continuous process run at a temperature of between —100° C. and 500° C.  
     
     
         175 - 190  canceled.