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 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. 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. The inventive catalysts maintains the functional group tolerance of previously described ruthenium complexes while having enhanced metathesis activity that compares favorably to prior art tungsten and molybdenum systems.

1 - 64 . (canceled) 
     
     
         65 . A composition of matter 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 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  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.