Imidazolidine-based metal carbene metathesis catalysts

Abstract

The present invention relates to novel metathesis catalysts with an imidazolidine-based ligand and to methods for making and using the same. The inventive catalysts are wherein: M is ruthenium or osmium; X and X 1 are each independently an anionic ligand; L is a neutral electron donor ligand; and, R, R 1 R 6 , R 7 , R 8 , and R 9 are each independently hydrogen or a substituent selected for the group consisting of C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, aryl, C 1 -C 20 alkoxycarbonyl, C 1 -C 20 alkylthiol, aryl thiol, C 1 -C 20 alkylsulfonyl and C 1 -C 20 alkylsulfinyl, the substituted optionally substituted with one or more moieties selected from the group consisting of C 1 -C 20 alkyl, C 1 -C 10 alkoxy, aryl, and a functional group. The inclusion of an imidazolidine ligand to the previously described ruthenium or osmium catalysts has been found to dramatically improve the properties of these complexes.

What is claimed is: 
     
         1 . A compound of the formula 
       
         
           
           
               
               
           
         
       
       wherein:
 M is ruthenium or osmium; 
 X and X 1  are each independently an anionic ligand; 
 L is a neutral electron donor ligand; and, 
 R, R 1 , R 6 , R 7 , R 8 , and R 9  are each independently hydrogen or a substituent selected from the group consisting of C 1 -C 20  alkyl, C 2 -C 20  alkenyl, C 2 -C 20  alkynyl, aryl, C 1 -C 20  carboxylate, C 1 -C 20  alkoxy, C 2 -C 20  alkenyloxy, C 2 -C 20  alkynyloxy, aryloxy, C 2 -C 20  alkoxycarbonyl, C 1 -C 20  alkylthiol, aryl thiol, C 1 -C 20  alkylsulfonyl and C 1 -C 20  alkylsulfinyl, the substituent optionally substituted with one or more moieties selected from the group consisting of C 1 -C 10  alkyl, C 1 -C 10  alkoxy, aryl, and a functional group selected from the group consisting of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, and halogen. 
 
     
     
         2 . A composition of matter comprising a compound having the formula: 
       
         
           
           
               
               
           
         
       
       where:
 M is Ru or Os; 
 X and X 1  are each independently an anionic ligand; 
 P is phosphorus; 
 R g , R h  and R i  are each independently:
 (1) a C 1-10  alkyl group, 
 (2) a C 3-10  cycloalkyl group or 
 (3) a C 5-20  aryl group; 
 
 R, R 6 , R 7 , R 8 , and R 9  are each independently:
 (1) hydrogen, 
 (2) a C 1-10  alkyl group, 
 (3) a C 7-20  alkenyl group, 
 (4) a C 2-20  alkynyl group, 
 (5) an aryl group, 
 (6) a C 1-20  carboxylate group, 
 (7) a C 1-20  alkoxy group, 
 (8) a C 2 - 7 0 alkenyloxy group, 
 (9) a C 2-20  alkynyloxy group, 
 (10) an aryloxy group, 
 (11) a C 2-20  alkoxycarbonyl group, 
 (12) a C 1-20  alkylthiol group, 
 (13) a C 1-20  alkylsulfonyl group, 
 (14) a C 1-20  alkylsulfinyl group, 
 
 where each of R, R 6 , R 7 , R 8 , and R 9  is optionally substituted with
   (a) halogen,   (b) a C 1-10  alkyl group,   (c) a C 1-10  alkoxy group,   (d) an aryl group   (e) a hydroxyl group,   (f) a thiol group,   (g) a thioester group,   (h) a ketone group,   (i) an aldehyde group,   (j) an ester group,   (k) an ether group,   (l) an amino group,   (m) an amido group,   (n) an imino group,   (o) a nitro group,   (p) a carboxylic acid group,   (q) a disulfide group,   (r) a carbonate group,   (s) an isocyanate group,   (t) a carbodiimide group,   (u) a carboalkoxy group, or   (v) a carbamate group.   
 
 
     
     
         3 . An olefin metathesis catalyst wherein the metathesis catalyst has the following structure: 
       
         
           
           
               
               
           
         
       
       wherein,
 M is ruthenium or osmium: 
 X and X 1  are each independently an anionic ligand; 
 L 1  is an imidazolidine ligand; 
 L is a neutral electron donor ligand; and 
 R and R 1  are each independently hydrogen, C 1-10  alkyl, C 2-20  alkenyl, C 2-20  alkynyl, aryl, C 1-20  carboxylate, C 1-20  alkoxy, C 2-20  alkenyloxy, C 2-20  alkynyloxy, aryloxy, C 2-20  alkoxycarbonyl, C 1-20  alkylthiol, aryl thiol, C 1-20  alkylsulfonyl, and C 1-20  alkylsulfinyl, and wherein each of R and R 1  is optionally substituted with halogen. C 1-10  alkyl, C 1-10  alkoxy, aryl, hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amino, amido, imino, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, or carbamate. 
 
     
     
         4 . The metathesis catalyst of  claim 3 , wherein the imidazolidine ligand has the following structure: 
       
         
           
           
               
               
           
         
       
       wherein,
 R 6 , R 7 , R 8 , and R 9  are each independently hydrogen, C 1-10  alkyl, C 2-20  alkenyl, C 2-20  alkynyl, aryl, C 1-20  carboxylate, C 1-20  alkoxy, C 2-20  alkenyloxy, C 2-20  alkynyloxy, aryloxy, C 2-20  alkoxycarbonyl, C 1-20  alkylthiol, aryl thiol, C 1-20  alkylsulfonyl, and C 1-20  alkylsulfinyl, and wherein each of R 6 , R 7 , R 8 , and R 9  is optionally substituted with halogen, C 1-10  alkyl, C 1-10  alkoxy, aryl, hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amino, amido, imino, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, or carbamate. 
 
     
     
         5 . The metathesis catalyst of  claim 3 , wherein at least one of L, L 1 , R, R 1 , X, and X 1  may be linked with at least one of L, L 1 , R, R 1 , X, and X 1  to form a bonded ligand array. 
     
     
         6 . The metathesis catalyst of  claim 3 , wherein L may be bonded together with one of X and X 1  to form a bidentate ligand. 
     
     
         7 . The metathesis catalyst of  claim 3 , wherein L may be bonded together with one of R and R 1  to form a bidentate ligand. 
     
     
         8 . The metathesis catalyst of  claim 3 , wherein R and R 1  may be bonded together. 
     
     
         9 . The metathesis catalyst of  claim 3 , wherein the metathesis catalyst has the following structure: 
       
         
           
           
               
               
           
         
       
       wherein,
 M is ruthenium or osmium; 
 X and X 1  are each independently an anionic ligand; 
 L is a neutral electron donor ligand; and 
 R, R 1 , R 6 , R 7 , R 8 , and R 9  are each independently hydrogen, C 1-10  alkyl, C 2-20  alkenyl, C 2-20  alkynyl, aryl, C 1-20  carboxylate, C 1-20  alkoxy, C 2-20  alkenyloxy, C 2-20  alkynyloxy, aryloxy, C 2-20  alkoxycarbonyl, C 1-20  alkylthiol, aryl thiol, C 1-20  alkylsulfonyl, and C 1-20  alkylsulfinyl, and wherein each of R and R 1  is optionally substituted with halogen, C 1-10  alkyl, C 1-10  alkoxy, aryl, hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amino, amido, imino, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, or carbamate. 
 
     
     
         10 . The metathesis catalyst of  claim 9 , wherein at least one of L, L 1 , R, R 1 , R 8 , R 9 , X, and X 1  may be linked with at least one of L, L 1 , R, R 1 , R 8 , R 9 , X, and X 1  to form a bonded, bidentate, or multidentate ligand array. 
     
     
         11 . The metathesis catalyst of  claim 9 , wherein L may be bonded together with one of X and X 1  to form a bidentate ligand. 
     
     
         12 . The metathesis catalyst of claim herein L may be bonded together with one of R and R 1  to form a bidentate ligand. 
     
     
         13 . The metathesis catalyst of  claim 9 , wherein R and R 1  may be bonded together. 
     
     
         14 . The metathesis catalyst of  claim 3 , wherein the metathesis catalyst has the following structure: 
       
         
           
           
               
               
           
         
       
       wherein,
 M is Ru or Os; 
 X and X 1  are each independently an anionic ligand; 
 P is phosphorus; 
 R g , R h  and R i  are each independently:
 (1) a C 1-10  alkyl group, 
 (2) a C 3-10  cycloalkyl group or 
 (3) a C 5-20  aryl group; 
 
 R, R 6 , R 7 , R 8 , and R 9  are each independently:
 (1) hydrogen, 
 (2) a C 1-10  alkyl group, 
 (3) a C 2-20  alkenyl group, 
 (4) a C 2-20  alkynyl group, 
 (5) an aryl group, 
 (6) a C 1-20  carboxylate group, 
 (7) a C 1-20  alkoxy group, 
 (8) a C 2-20  alkenyloxy group, 
 (9) a C 2-20  alkynyloxy group, 
 (10) an aryloxy group, 
 (11) a C 2-20  alkoxycarbonyl group, 
 (12) a C 1-20  alkylthiol group, 
 (13) a C 1-20  m alkylsulfonyl group, 
 (14) a C 1-20  alkylsulfinyl group, 
 
 where each of R, R 6 , R 7 , R 8 , and R 9  is optionally substituted with
   (a) halogen,   (b) a C 1-10  alkyl group,   (c) a C 1-10  alkoxy group,   (d) an aryl group   (e) a hydroxyl group,   (f) a thiol group,   (g) a thioester group,   (h) a ketone group,   (i) an aldehyde group,   (j) an ester group,   (k) an ether group.   (l) an amino group,   (m) an amino group,   (n) an imino group,   (o) a nitro group,   (p) a carboxylic acid group,   (q) a disulfide group,   (r) a carbonate group,   (s) an isocyanate group,   (t) a carbodiimide group,   (u) a carboalkoxy group, or   (v) a carbamate group.