Imidazolidine-based metal carbene metathesis catalysts
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. 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. The compound as in claim 1 wherein:
M is ruthenium;
L is selected from the group consisting of phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, arsine, stibine, ether, amine, amide, imine, sulfoxide, carboxyl, nitrosyl, pyridine, and thioether; and,
X and X 1 are each independently hydrogen, halide, or a substituent selected from the group consisting of C 1 -C 20 alkyl, aryl, C 1 -C 20 alkoxide, aryloxide, C 3 -C 20 alkyldiketonate, aryldiketonate, C 1 -C 20 carboxylate, arylsulfonate, C 1 -C 20 alkylsulfonate, C 1 -C 20 alkylthio, 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 halide.
3. The compound as in claim 1 wherein:
M is ruthenium;
X and X 1 are each independently selected from the group consisting of halide, CF 3 CO 2 , CH 3 CO 2 , CFH 2 CO 2 , (CH 3 ) 3 CO, (CF 3 ) 2 (CH 3 )CO, (CF 3 )(CH 3 ) 2 CO, PhO, MeO, EtO, tosylate, mesylate, and trifluoromethanesulfonate;
L is a phosphine of the formula PR 3 R 4 R 5 , where R 3 , R 4 , and R 5 are each independently aryl, C 1 -C 10 alkyl, or cycloalkyl;
R is hydrogen; and,
R 1 is phenyl or vinyl, optionally substituted with one or more moieties selected from the group consisting of C 1 -C 5 alkyl, C 1 -C 5 alkoxy, phenyl, 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.
4. The compound as in claim 3 wherein
X and X 1 are each chloride;
L is selected from the group consisting of —P(cyclohexyl) 3 , —P(cyclopentyl) 3 , —P(isopropyl) 3 , and —P(phenyl) 3 ; and,
R 1 is phenyl or —C═C(CH 3 ) 2 .
5. The compound as in claim 4 wherein R 6 and R 7 together form a cycloalkyl or an aryl.
6. The compound as in claim 4 wherein R 6 and R 7 together form a cyclopentyl or a cyclohexyl moiety.
7. The compound as in claim 4 wherein R 6 and R 7 are the same and are hydrogen or phenyl.
8. The compound as in claim 4 wherein R 8 and R 9 are each independently a substituted or unsubstituted aryl.
9. The compound as in claim 4 wherein R 8 and R 9 are the same and are phenyl.
10. The compound as in claim 4 wherein R 8 and R 9 are each independently of the formula
wherein
R 10 , R 11 , and R 12 are each independently hydrogen, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, aryl, or a functional group selected from hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, and halogen.
11. The compound as in claim 10 wherein R 10 , R 11 , and R 12 are each independently hydrogen, methyl or isopropyl.
12. A compound of the formula
wherein:
X and X 1 are each chloride;
L is selected from the group consisting of —P(cyclohexyl) 3 , —P(cyclopentyl) 3 , —P(isopropyl) 3 , and —P(phenyl) 3 ;
R is hydrogen;
R 1 is phenyl or vinyl, optionally substituted with one or more moieties selected from the group consisting of C 1 -C 5 alkyl, C 1 -C 5 alkoxy, phenyl, 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;
R 6 and R 7 are each independently hydrogen, phenyl, or together form a cycloalkyl or an aryl 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; and
R 8 and R 9 are each is independently C 1 -C 10 alkyl or aryl optionally substituted with C 1 -C 5 alkyl, C 1 -C 5 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.
13. The compound as in claim 12 wherein R 8 and R 9 are each is independently a cycloalkyl or a phenyl optionally substituted with C 1 -C 5 alkyl, C 1 -C 5 alkoxy, or halogen.
14. The compound as in claim 12 wherein R 8 and R 9 are each independently of the formula
wherein
R 10 , R 11 , and R 12 are each independently hydrogen, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, aryl, or a functional group selected from hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, and halogen.
15. The compound as in claim 14 wherein R 10 , R 11 , and R 12 are the same and are each methyl.
16. The compound as in claim 12 selected from the group consisting of
17. A compound of the formula
wherein:
X and X 1 are each chloride;
L is selected from the group consisting of —P(cyclohexyl) 3 , —P(cyclopentyl) 3 , —P(isopropyl) 3 , and —P(phenyl) 3 ;
R is hydrogen;
R 1 is phenyl or —C═C(CH 3 ) 2 ;
R 6 and R 7 are each independently hydrogen, phenyl, or together form a cyclopentyl or cyclohexyl; and
R 8 and R 9 are each is independently of the formula
wherein
R 10 , R 11 , and R 12 are each independently hydrogen, methyl, ethyl, propyl, isopropyl, hydroxyl, and halogen.
18. A method for making a compound of the formula
comprising contacting
with
wherein:
M is ruthenium or osmium;
X and X 1 are each independently an anionic ligand;
L is a neutral electron donor ligand;
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; and,
R 13 is C 1 -C 20 alkyl or aryl.
19. The method as in claim 18 wherein
M is ruthenium;
X and X 1 are each chloride;
L is selected from the group consisting of —P(cyclohexyl) 3 , —P(cyclopentyl) 3 , —P(isopropyl) 3 , and —P(phenyl) 3 ;
R is hydrogen;
R 1 is phenyl or —C═C(CH 3 ) 2 ;
R 6 and R 7 are each independently hydrogen, phenyl, or together form a cyclopenyl or cyclohexyl; and,
R 8 and R 9 are each independently a substituted or unsubstituted aryl.
20. The method as in claim 19 wherein R 13 is t-butyl.
21. The method as in claim 18 wherein
M is ruthenium;
X and X 1 are each chloride;
L is selected from the group consisting of —P(cyclohexyl) 3 , —P(cyclopentyl) 3 , —P(isopropyl) 3 , and —P(phenyl) 3 ;
R is hydrogen;
R 1 is phenyl or —C═C(CH 3 ) 2 ;
R 6 and R 7 together form a cycloalkyl group; and
R 8 and R 9 are the same and are each of the formula
wherein
R 10 , R 11 , and R 12 are each independently hydrogen, methyl, ethyl, propyl, isopropyl, hydroxyl, and halogen.
22. The method as in claim 21 wherein
is optically active.
23. A method for making a metathesis catalyst comprising contacting a compound of the formula
with an imidazolidine whereby the imidazolidine replaces one of the L ligands 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 and R 1 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.
24. The method as in claim 23 wherein the imidazolidine is formed by
contacting a secondary diamine with ammonium tetrafluoroborate to form an imidazolium salt; and
contacting the imidazolium salt with an alkyloxide to form the imidazolidine.
25. The method as in claim 24 wherein the secondary diamine is formed by
contacting a diketone with an amine to form a diimine and
hydrogenating the diimine to form the secondary di-amine.
26. The method as in claim 24 wherein the alkyloxide is t-butoxide.
27. The method as in claim 24 wherein the imidazolidine is of the formula
wherein
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; and,
R 13 is C 1 -C 20 alkyl or aryl.
28. The method as in claim 27 wherein
M is ruthenium;
X and X 1 are each chloride;
L is selected from the group consisting of —P(cyclohexyl) 3 , —P(cyclopentyl) 3 , —P(isopropyl) 3 , and —P(phenyl) 3 ;
R is hydrogen; and
R 1 is phenyl or vinyl, optionally substituted with one or more moieties selected from the group consisting of C 1 -C 5 alkyl, C 1 -C 5 alkoxy, phenyl, 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.
29. The method as in claim 28 wherein R 1 is phenyl or —C═C(CH 3 ) 2 and R 13 is t-butoxide.
30. The method as in claim 28 wherein
R 6 and R 7 are each independently hydrogen, phenyl, or together form a cycloalkyl or an aryl 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; and
R 8 and R 9 are each independently either substituted or unsubstituted aryl.
31. The method as in claim 30 wherein R 8 and R 9 are each is independently of the formula
wherein
R 10 , R 11 , and R 12 are each independently hydrogen, methyl, ethyl, propyl, isopropyl, hydroxyl, and halogen.
32. A method for performing a metathesis reaction comprising contacting an olefin with 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.
33. The method as in claim 32 wherein:
M is ruthenium;
X and X 1 are each chloride;
L is selected from the group consisting of —P(cyclohexyl) 3 , —P(cyclopentyl) 3 , —P(isopropyl) 3 , and —P(phenyl) 3 ;
R is hydrogen;
R 1 is phenyl or vinyl, optionally substituted with one or more moieties selected from the group consisting of C 1 -C 5 alkyl, C 1 -C 5 alkoxy, phenyl, 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;
R 6 and R 7 are each independently hydrogen, phenyl, or together form a cycloalkyl or an aryl 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; and
R 8 and R 9 are each is independently C 1 -C 10 alkyl or aryl optionally substituted with C 1 -C 5 alkyl, C 1 -C 5 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.
34. The method as in claim 32 wherein the compound is selected from the group consisting of
35. The method as in claim 33 wherein the olefin is a cyclic olefin.
36. 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 selected from the group consisting of phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, arsine, stibine, ether, amine, amide, imine, sulfoxide, carboxyl, nitrosyl, pyridine, and thioether; 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, cycloalkyl, 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 alkylthio, 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.
37. A method for making a metathesis catalyst comprising:
forming an imidazolidine by contacting a secondary diamine with ammonium tetrafluoroborate to form an imidazolium salt; and contacting the imidazolium salt with an alkyloxide; and
contacting a compound of the formula
with the imidazolidine, whereby the imidazolidine replaces one of the L ligands 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 and R 1 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 alkylthio, 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.
38. A method for performing a metathesis reaction comprising contacting an olefin with a compound of the formula
wherein:
M is ruthenium or osmium;
X and X 1 are each independently an anionic ligand;
L is selected from the group consisting of phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, arsine, stibine, ether, amine, amide, imine, sulfoxide, carboxyl, nitrosyl, pyridine, and thioether;
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 alkylthio, 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.
39. A compound of the formula
wherein:
M is ruthenium or osmium;
X and X 1 are each independently an anionic ligand;
L is a saturated N-heterocyclic carbene 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 alkylthio, 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.
40. 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, provided that L is not an unsaturated N-heterocyclic carbene of the following formula:
; 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 alkylthio, 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.
41. The method of claim 32 wherein the olefin is cyclic or acyclic.
42. The method of claim 32 wherein the olefin bears at least one electron withdrawing group.
43. The method of claim 42 wherein the electron withdrawing group is selected from the group consisting of esters, aldehydes, ketones, and phosphonates.
44. The compound of claim 1 wherein at least one moiety selected from the group consisting of L, R, R 1 , X and X 1 is linked with at least one other moiety selected from the group consisting of L, R, R 1 , X and X 1 , to form a bonded ligand array.
45. A composition comprising:
(a) a compound of the formula
wherein:
M is Ru or Os;
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; and
(b) an unsaturated carbonyl compound.
46. The composition of claim 45 wherein the carbonyl compound is conjugated.
47. The composition of claim 45 wherein (b) is selected from the group consisting of ketones, aldehydes, amides, and carboxylic acids.
48. The composition of claim 45 wherein (b) is an acrylate.
49. The composition of claim 45 wherein (b) is methyl methacrylate.
50. The composition of claim 45 wherein M is Ru, X and X 1 are each Cl, L is a phosphine of the formula PR 3 R 4 R 5 , where R 3 , R 4 , and R 5 are each independently aryl, C 1 -C 10 alkyl, or cycloalkyl; R is hydrogen and R 1 is substituted or unsubstituted phenyl or vinyl; and the unsaturated carbonyl compound is an acrylate.
51. The compound of claim 1 , wherein L is bonded together with one of X and X 1 to form a bidentate ligand.
52. The compound of claim 1 , wherein L is bonded together with one of R and R 1 are bonded together to form a bidentate ligand.
53. The compound of claim 1 , wherein R and R 1 are bonded together.
54. 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;
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; and
at least one moiety selected from the group consisting of L, R, R 1 , X and X 1 is linked with at least one other moiety selected from the group consisting of L, R, R 1 , X and X 1 , to form a bonded ligand array.
55. The method of claim 23 , wherein at least one moiety selected from the group consisting of L, R, R 1 , X, and X 1 is linked with at least one other moiety selected from the group consisting of L, R, R 1 , X and X 1 , to form a bonded ligand array.
56. The method of claim 23 , wherein L is bonded together with one of X and X 1 to form a bidentate ligand.
57. The method of claim 23 , wherein L is bonded together with of R and R 1 to form a bidentate ligand.
58. The method of claim 23 , wherein R and R 1 are bonded together.
59. The method of claim 32 , wherein at least one moiety selected from the group consisting of L, R, R 1 , R 8 , R 9 , X and X 1 is linked with at least one other moiety selected from the group consisting of L, R, R 1 , R 8 , R 9 , X and X 1 , to form a bonded, bidentate, or multidentate ligand array.
60. The method of claim 32 , wherein L is bonded together with one of X and X 1 are bonded together to form a bidentate ligand.
61. The method of claim 32 , wherein L is bonded together with one of R and R 1 to form a bidentate ligand.
62. The method of claim 32 , wherein R and R 1 are bonded together.
63. A method for synthesizing a cyclic olefin by ring-closing metathesis, the method comprising the step of contacting an acyclic olefin with a compound of the formula
wherein:
M is Ru or Os;
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.
64. The method of claim 58 wherein the acyclic olefin is a C 5 -C 60 acyclic olefin.