Method for in-situ formation of metathesis catalysts

Abstract

Synthetic methods for the in-situ formation of olefin metathesis catalysts are disclosed, as well as the use of such catalysts in metathesis reactions of olefins and olefin compounds. In one aspect, a method is provided for synthesizing an organometallic compound of the formula comprising contacting a precursor compound of the formula (X 1 X 2 ML j L 1 k L 3 m ) i with an acetylenic compound comprising a chelating moiety, optionally, in the presence of a neutral electron donor, wherein M is a Group 8 transition metal, L, L 1 , L 2 , and L 3 are neutral electron donors, X 1 and X 2 are anionic ligands, j is 1, 2, or 3; k is zero, 1, or 2; m is zero or 1; n is 1 or 2; and i is an integer; with the proviso that k is zero when the precursor compound is contacted with the acetylenic compound in the presence of the neutral electron donor, and R 1 and R 2 are independently selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups, wherein R 1 and R 2 are linked and together form one or more cyclic groups, R 2 and L 2 are linked and together form one or more cyclic groups, and any other two or more of X 1 , X 2 , L 1 , L 2 , L 3 , R 1 , and R 2 can be taken together to form one or more cyclic groups. The invention has utility in the fields of catalysis, organic synthesis, polymer chemistry, and industrial and fine chemicals chemistry.

1 . A method for synthesizing an organometallic compound of the formula 
       
         
           
           
               
               
           
         
         comprising contacting a precursor compound of the formula (X 1 X 2 ML j L 1   k L 3   m ) i  with an acetylenic compound comprising a chelating moiety, optionally, in the presence of a neutral electron donor L 1 ; 
         wherein, 
         M is a Group 8 transition metal; 
         L, L 1 , L 2 , and L 3  are neutral electron donors; 
         j is 1, 2, or 3; k is zero, 1, or 2; m is zero or 1; n is 1 or 2; and i is an integer; with the proviso that k is zero when the precursor compound is contacted with the acetylenic compound in the presence of the neutral electron donor L 1 ; 
         X 1  and X 2  are anionic ligands; and 
         R 1  and R 2  are independently selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups, wherein R 1  and R 2  are linked and together form one or more cyclic groups, R 2  and L 2  are linked and together form one or more cyclic groups, and any other two or more of X 1 , X 2 , L 1 , L 2 , L 3 , R 1 , and R 2  can be taken together to form one or more cyclic groups. 
       
     
     
         2 . The method of  claim 1 , wherein M is Ru or Os. 
     
     
         3 . The method of  claim 1 , wherein L 1 , L 2 , and L 3  are independently selected from phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, arsine, stibine, ether, amine, amide, imine, sulfoxide, carboxyl, nitrosyl, pyridine, substituted pyridine, imidazole, substituted imidazole, pyrazine, thioether, and thiocarbonyl. 
     
     
         4 . The method of  claim 3 , wherein the phosphine is of the formula PR a R b R c , wherein R a , R b , and R c  are each independently selected from aryl, substituted aryl, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heterocycles, and substituted heterocycles. 
     
     
         5 . The method of  claim 1 , wherein X 1  and X 2  are independently selected from hydrogen, halide, C 1 -C 20  alkyl, C 5 -C 20  aryl, C 1 -C 20  alkoxy, C 5 -C 20  aryloxy, C 2 -C 20  alkoxycarbonyl, C 6 -C 20  aryloxycarbonyl, C 2 -C 20  acyl, C 2 -C 20  acyloxy, C 1 -C 20  alkylsulfonato, C 5 -C 20  arylsulfonato, C 1 -C 20  alkylsulfanyl, C 5 -C 20  arylsulfanyl, C 1 -C 20  alkylsulfinyl, or C 5 -C 20  arylsulfinyl, any of which, with the exception of hydrogen and halide, are optionally further substituted with one or more groups selected from halide, C 1 -C 6  alkyl, C 1 -C 6  alkoxy, and C 5 -C 20  aryl. 
     
     
         6 . The method of  claim 1 , wherein the acetylenic compound comprising a chelating moiety is a compound having the structure 
       
         
           
           
               
               
           
         
         wherein,
 J is a leaving group selected from hydroxyl, halide, ester, perhalogenated phenyl, acetate, benzoate, C 2 -C 6  acyl, C 2 -C 6  alkoxycarbonyl, C 1 -C 6  alkyl, phenoxy, C 1 -C 6  alkoxy, C 1 -C 6  alkylsulfanyl, aryl, and C 1 -C 6  alkylsulfonyl; 
 R 5 , R 6 , R 7 , R 8 , and R 9  are each independently selected from hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroatom containing alkenyl, heteroalkenyl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, carbonyl, alkylamino, alkylthio, aminosulfonyl, monoalkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, hydroxyl, ester, ether, amine, imine, amide, halogen-substituted amide, trifluoroamide, sulfide, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, borate, and any combination of R 5 , R 6 , R 7 , R 8 , and R 9  can be linked to form one or more cyclic groups; and wherein R 5 , R 6 , R 7 , R 8 , and R 9  may contain -T-(Z) n* , wherein, 
 T is a heteroatom selected from N, O, S, and P; 
 Z is selected from hydrogen, alkyl, aryl, functionalized alkyl, and functionalized aryl, wherein the functional group(s) are independently selected from alkyl, aryl, alkoxy, aryloxy, halogen, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, hydroxyl, ester, ether, amine, imine, amide, trifluoroamide, sulfide, disulfide, carbamate, silane, siloxane, phosphine, phosphate, or borate; and n* is 1 or 2, such that n* is 1 for the divalent heteroatoms O or S, and n* is 2 for the trivalent heteroatoms N or P; and 
 R 10  is selected from hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroatom containing alkenyl, heteroalkenyl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, carbonyl, alkylamino, alkylthio, aminosulfonyl, monoalkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, hydroxyl, ester, ether, amine, imine, amide, halogen-substituted amide, trifluoroamide, sulfide, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, or borate, and wherein when R 10  is aryl or heteroaryl, R 10  may be substituted with any combination of R 5 , R 6 , R 7 , R 8  and R 9  and can be linked with any of R 5 , R 6 , R 7 , R 8 , and R 9  to form one or more cyclic groups. 
 
       
     
     
         7 . The method of  claim 6 , wherein the acerylenic compound comprising a chelating moiety is a compound of the formula 
       
         
           
           
               
               
           
         
         wherein,
 T, Z, and n* are as defined in  claim 6 ; 
 
         n1 is an integer from 1 to 5; 
         n2 is an integer from 0 to 5; and 
         R* is selected from R 5 , R 6 , R 7 , R 8 , and R 9 , or combinations thereof, as defined in  claim 6 . 
       
     
     
         8 . The method of  claim 1 , wherein the organometallic compound is of the formula 
       
         
           
           
               
               
           
         
         wherein, M, L 1 , L 3 , X 1 , X 2 , R 1 , R 5 , R 6 , R 7 , R 8 , n, and m are as defined in  claim 1 ;
 T is a heteroatom selected from N, O, S, and P; 
 Z is selected from hydrogen, alkyl, aryl, functionalized alkyl, and functionalized aryl, wherein the functional group(s) are independently selected from alkyl, aryl, alkoxy, aryloxy, halogen, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, hydroxyl, ester, ether, amine, imine, amide, trifluoroamide, sulfide, disulfide, carbamate, silane, siloxane, phosphine, phosphate, or borate; and 
 n* is 1 or 2, such that n* is 1 for the divalent heteroatoms O or S, and n* is 2 for the trivalent heteroatoms N or P. 
 
       
     
     
         9 . A compound of the formula 
       
         
           
           
               
               
           
         
         wherein,
 M is a Group 8 transition metal; 
 L 1 , L 2 , and L 3  are neutral electron donor ligands; 
 m is zero or 1; and n is 1 or 2; 
 X 1  and X 2  are anionic ligands; and 
 R 1  and R 2  are independently selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups, wherein R 1  and R 2  are linked and together form one or more cyclic groups, R 2  and L 2  are linked and together form one or more cyclic groups, and any other two or more of X 1 , X 2 , L 1 , L 2 , L 3 , R 1 , and R 2  can be taken together to form one or more cyclic groups. 
 
       
     
     
         10 . The compound of  claim 9 , wherein M is Ru or Os. 
     
     
         11 . The compound of  claim 9 , wherein L 1 , L 2 , and L 3  are independently selected from phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, arsine, stibine, ether, amine, amide, imine, sulfoxide, carboxyl, nitrosyl, pyridine, substituted pyridine, imidazole, substituted imidazole, pyrazine, thioether, and thiocarbonyl. 
     
     
         12 . The compound of  claim 11 , wherein the phosphine is of the formula PR a R b R c , wherein R a , R b , and R c  are each independently selected from aryl, substituted aryl, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heterocycles, and substituted heterocycles. 
     
     
         13 . The compound of  claim 9 , wherein X 1  and X 2  are independently selected from hydrogen, halide, C 1 -C 20  alkyl, C 5 -C 20  aryl, C 1 -C 20  alkoxy, C 5 -C 20  aryloxy, C 2 -C 20  alkoxycarbonyl, C 6 -C 20  aryloxycarbonyl, C 2 -C 20  acyl, C 2 -C 20  acyloxy, C 1 -C 20  alkylsulfonato, C 5 -C 20  arylsulfonato, C 1 -C 20  alkylsulfanyl, C 5 -C 20  arylsulfanyl, C 1 -C 20  alkylsulfinyl, or C 5 -C 20  arylsulfinyl, any of which, with the exception of hydrogen and halide, are optionally further substituted with one or more groups selected from halide, C 1 -C 6  alkyl, C 1 -C 6  alkoxy, and C 5 -C 20  aryl. 
     
     
         14 . A compound of the formula 
       
         
           
           
               
               
           
         
         wherein,
 M is a Group 8 transition metal; 
 L 1 , L 2 , and L 3  are neutral electron donor ligands; 
 m is zero or 1; and n is 1 or 2; 
 X 1  and X 2  are anionic ligands; and 
 R 1  and R 2  are independently selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups, wherein R 1  and R 2  are linked and together form one or more cyclic groups, R 2  and L 2  are linked and together form one or more cyclic groups, and any other two or more of X 1 , X 2 , L 1 , L 2 , L 3 , R 1 , and R 2  can be taken together to form one or more cyclic groups; 
 wherein said compound is synthesized according to the method of  claim 1 . 
 
       
     
     
         15 . The compound of  claim 9 , wherein the compound is of the formula 
       
         
           
           
               
               
           
         
         wherein,
 M, L 1 , L 3 , X 1 , X 2 , R 1 , n, and m are as defined in  claim 9 ; 
 R 5 , R 6 , R 7 , and R 8  are each independently selected from hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroatom containing alkenyl, heteroalkenyl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, carbonyl, alkylamino, alkylthio, aminosulfonyl, monoalkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, hydroxyl, ester, ether, amine, imine, amide, halogen-substituted amide, trifluoroamide, sulfide, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, borate, wherein R 1  and R 8  are linked and together form one or more cyclic groups, and any combination of R 1 , R 5 , R 6 , R 7 , and R 8  can be linked to form one or more cyclic groups; 
 T is a heteroatom selected from N, O, S, and P; 
 Z is selected from hydrogen, alkyl, aryl, functionalized alkyl, and functionalized aryl, wherein the functional group(s) are independently selected from alkyl, aryl, alkoxy, aryloxy, halogen, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, hydroxyl, ester, ether, amine, imine, amide, trifluoroamide, sulfide, disulfide, carbamate, silane, siloxane, phosphine, phosphate, or borate; and 
 n* is 1 or 2, such that n* is 1 for the divalent heteroatoms O or S, and n* is 2 for the trivalent heteroatoms N or P. 
 
       
     
     
         16 . The compound of  claim 15 , wherein R 1  and R 8  are linked to form a compound of the formula 
       
         
           
           
               
               
           
         
         wherein,
 M is a Group 8 transition metal; 
 L 1  and L 3  are neutral electron donor ligands; 
 X 1  and X 2  are anionic ligands; 
 R 1  is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups; 
 n is 1 or 2 and m is zero or 1; 
 R 5 , R 6 , R 7 , R 8 , T, Z, and n* are as defined in  claim 15 ; and 
 R 10  is selected from hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroatom containing alkenyl, heteroalkenyl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, carbonyl, alkylamino, alkylthio, aminosulfonyl, monoalkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, hydroxyl, ester, ether, amine, imine, amide, halogen-substituted amide, trifluoroamide, sulfide, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, or borate, and wherein when R 10  is aryl or heteroaryl, R 10  may be substituted with any combination of R 5 , R 6 , R 7 , and R 8 , and further wherein R 10  can be linked with any of R 5 , R 6 , and R 7  to form one or more cyclic groups. 
 
       
     
     
         17 . A method of performing a metathesis reaction, comprising contacting the compound of  claim 9  with an olefin.