Catalyst complex with carbene ligand
Catalytic complexes including a metal atom having anionic ligands, at least one nucleophilic carbene ligand, and an alkylidene, vinylidene, or allenylidene ligand. The complexes are highly stable to air, moisture and thermal degradation. The complexes are designed to efficiently carry out a variety of olefin metathesis reactions.
1. A catalytic complex of the formula:
wherein M is Os or Ru;
R and R 1 are independently selected from the group consisting of hydrogen, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 2 -C 20 alkoxycarbonyl, aryl, C 1 -C 20 carboxylate, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, aryloxy, C 1 -C 20 alkylthio, C 1 -C 20 alkylsulfonyl, and C 1 -C 20 alkylsulfinyl, each R and R 1 optionally being substituted with C 1 -C 5 alkyl, halogen, C 1 -C 10 alkoxy, or with a phenyl group substituted with halogen, C 1 -C 5 alkyl or C 1 -C 5 alkoxy, or with a functional group;
X and X 1 are independently selected from the group consisting of anionic ligands;
L is selected from the group consisting of phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, ether, amine, amide, sulfoxide, carbonyl, nitrosyl, pyridine and thioether; and
L 1 is a nucleophilic carbene.
2. A catalytic complex according to claim 1 , wherein L is a phosphine.
3. A catalytic complex according to claim 1 , wherein at least 2 of X, X 1 , L or L 1 are bonded together to form a multidentate ligand.
4. A catalytic complex according to claim 1 , wherein said nucleophilic carbene is of the formula:
wherein
Y and Y 1 are independently selected from the group consisting of hydrogen, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 2 -C 20 alkoxycarbonyl, aryl, C 1 -C 20 carboxylate, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, and aryloxy, each Y and Y 1 optionally being substituted with C 1 -C 5 alkyl, halogen, C 1 -C 6 alkoxy, or with a phenyl group substituted with halogen, C 1 -C 5 alkyl or C 1 -C 5 alkoxyl; and
Z and Z 1 are independently selected from the group consisting of hydrogen, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 2 -C 20 alkoxycarbonyl, aryl, C 1 -C 20 carboxylate, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, and aryloxy, each Z and Z 1 optionally being substituted with C 1 -C 5 alkyl, halogen, C 1 -C 6 alkoxy, or with a phenyl group substituted with halogen, C 1 -C 5 alkyl or C 1 -C 5 alkoxy.
5. A catalytic complex of the formula:
wherein either or both of C 1 and C 2 are optionally absent;
M is selected from the group consisting of Os and Ru;
R and R 1 are independently selected from the group consisting of hydrogen, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 2 -C 20 alkoxycarbonyl, aryl, C 1 -C 20 carboxylate, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy aryloxy, C 1 -C 20 alkylthio, C 1 -C 20 alkylsulfonyl, and C 1 -C 20 alkylsulfinyl, each R and R 1 optionally being substituted with C 1 -C 5 alkyl, halogen, C 1 -C 10 alkoxy, or with a phenyl group substituted with halogen, C 1 -C 5 alkyl or C 1 -C 5 alkoxy, or with a functional group;
X is an anionic ligand;
L is a nucleophilic carbene;
Ar is an aryl substituent, bonded to M by an η 6 bond; and
A − is an inorganic anion or an organic anion.
6. A catalytic complex according to claim 5 , wherein said nucleophilic carbene is of the formula:
wherein
Y and Y 1 are independently selected from the group consisting of hydrogen, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 2 -C 20 alkoxycarbonyl, aryl, C 1 -C 20 carboxylate, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy and aryloxy, each Y and Y 1 optionally being substituted with C 1 -C 5 alkyl, halogen, C 1 -C 6 alkoxy, or with a phenyl group substituted with halogen, C 1 -C 5 alkyl or C 1 -C 5 alkoxyl; and
Z and Z 1 are independently selected from the group consisting of hydrogen, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 2 -C 20 alkoxycarbonyl, aryl, C 1 -C 20 carboxylate, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, and aryloxy, each Z and Z 1 optionally being substituted with C 1 -C 5 alkyl, halogen, C 1 -C 6 alkoxy, or with a phenyl group substituted with halogen, C 1 -C 5 alkyl or C 1 -C 5 alkoxy.
7. A method of making a nucleophilic carbene, said method comprising:
a) contacting a substituted or unsubstituted aniline with an approximately one-half equimolar amount of paraformaldehyde under an inert atmosphere to make a first reaction mixture;
b) heating said first reaction mixture until said paraformaldehyde dissolves;
c) adding an approximately one-half equimolar amount of a dialkoxyacetaldehyde to make a second reaction mixture; and
d) heating said second reaction mixture for a time and under conditions sufficient to make a nucleophilic carbene.
8. The method of claim 7 , wherein said aniline is 2,4,6-trimethylaniline.
9. The method of claim 7 , wherein said aniline is 2,6-diisopropylaniline.
10. The method of claim 7 , further comprising the step of hydrogenating the nucleophilic carbene to produce a non-aromatic nucleophilic carbene.
11. A method of performing ring closing metathesis, said method comprising contacting a diene with a catalytic complex under conditions appropriate, and for a time sufficient to produce a cyclic alkene, wherein the catalytic complex has the formula:
wherein M is Os or Ru;
wherein C 2 is optionally absent;
R and R 1 are independently selected from the group consisting of hydrogen, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 2 -C 20 alkoxycarbonyl, aryl, C 1 -C 20 carboxylate, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, aryloxy, C 1 -C 20 alkylthio, C 1 -C 20 alkylsulfonyl, and C 1 -C 20 alkylsulfinyl, each R and R′ optionally being substituted with C 1 -C 5 alkyl, halogen, C 1 -C 10 alkoxy, or with a phenyl group substituted with halogen, C 1 -C 5 alkyl or C 1 -C 5 alkoxy, or with a functional group;
X and X 1 are independently selected from the group consisting of anionic ligands;
L is selected from the group consisting of phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, ether, amine, amide, sulfoxide, carbonyl, nitrosyl, pyridine and thioether; and
L 1 is a nucleophilic carbene.
12. The method of claim 11 , wherein the nucleophilic carbene has the formula:
wherein
Y and Y 1 are independently selected from the group consisting of hydrogen, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 2 -C 20 alkoxycarbonyl, aryl, C 1 -C 20 carboxylate, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, and aryloxy, each Y and Y 1 optionally being substituted with C 1 -C 5 alkyl, halogen, C 1 -C 6 alkoxy, or with a phenyl group substituted with halogen, C 1 -C 5 alkyl or C 1 -C 5 alkoxy; and
Z and Z 1 are independently selected from the group consisting of hydrogen, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 2 -C 20 alkoxycarbonyl, aryl, C 1 -C 20 carboxylate, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, and aryloxy, each Z and Z 1 optionally being substituted with C 1 -C 5 alkyl, halogen, C 1 -C 6 alkoxy, or with a phenyl group substituted with halogen, C 1 -C 5 alkyl or C 1 -C 5 alkoxy.
13. A method of performing ring closing metathesis, said method comprising contacting a diene with a catalytic complex under conditions appropriate, and for a time sufficient to produce a cyclic alkene, wherein the catalytic complex has the formula:
wherein either or both of C 1 and C 2 are optionally absent;
M is selected from the group consisting of Os and Ru;
R and R 1 are independently selected from the group consisting of hydrogen, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 2 -C 20 alkoxycarbonyl, aryl, C 1 -C 20 carboxylate, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, aryloxy, C 1 -C 20 alkylthio, C 1 -C 20 alkylsulfonyl, and C 1 -C 20 alkylsulfinyl, each R and R 1 optionally being substituted with C 1 -C 5 alkyl, halogen, C 1 -C 10 alkoxy, or with a phenyl group substituted with halogen, C 1 -C 5 alkyl or C 1 -C 5 alkoxy, or with a functional group;
X is an anionic ligand;
L is a nucleophilic carbene;
Ar is an aryl substituent, bonded to M by an η 6 bond; and
A − is an inorganic anion or an organic anion.
14. The method of claim 13 , wherein the nucleophilic carbene has the formula:
wherein
Y and Y 1 dare independently selected from the group consisting of hydrogen, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 2 -C 20 alkoxycarbonyl, aryl, C 1 -C 20 carboxylate, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, and aryloxy, each Y and Y 1 optionally being substituted with C 1 -C 5 alkyl, halogen, C 1 -C 6 alkoxy, or with a phenyl group substituted with halogen, C 1 -C 5 alkyl or C 1 -C 5 alkoxy; and
Z and Z 1 are independently selected from the group consisting of hydrogen, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 2 -C 20 alkoxycarbonyl, aryl, C 1 -C 20 carboxylate, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, and aryloxy, each Z and Z 1 optionally being substituted with C 1 -C 5 alkyl, halogen, C 1 -C 6 alkoxy, or with a phenyl group substituted with halogen, C 1 -C 5 alkyl or C 1 -C 5 alkoxy.
15. The catalytic complex according to claim 1 , wherein X and X 1 are independently selected from the group consisting of halide, carboxylate, alkoxy, aryloxy, and alkyl sulfonate.
16. The catalytic complex according to claim 15 , wherein X and X 1 are both chloride.
17. The catalytic complex of claim 1 , wherein the nucleophilic carbene ligand comprises a carbene carbon further bonded to two heteroatoms having electronegativity greater than that of carbon, and wherein the heteroatoms are independently selected from the group consisting of nitrogen, oxygen, and sulfur.
18. The catalytic complex of claim 17 , wherein the nucleophilic carbene ligand comprises a saturated or unsaturated 1,3-diheterocyclic compound.
19. The catalytic complex of claim 1 , wherein the complex is linked to a solid support by means of a link between at least one of said anionic ligands and said solid support.
20. The catalytic complex according to claim 1 , wherein the complex is linked to a solid support by means of a link between the nucleophilic carbene and said solid support.
21. The catalytic complex according to claim 5 , wherein X is selected from the group consisting of halide, carboxylate, alkoxy, aryloxy, and alkyl sulfonate.
22. The catalytic complex according to claim 21 , wherein X is chloride.
23. The catalytic complex of claim 5 , wherein the nucleophilic carbene ligand comprises a carbene carbon further bonded to two heteroatoms having electronegativity greater than that of carbon, wherein the heteroatoms are independently selected from the group consisting of nitrogen, oxygen, and sulfur.
24. The catalytic complex of claim 23 , wherein the nucleophilic carbene ligand comprises a saturated or unsaturated 1,3-diheterocyclic compound.
25. The catalytic complex of claim 5 , wherein the complex is linked to a solid support by means of a link between said anionic ligand and said solid support.
26. The catalytic complex of claim 5 , wherein the complex is linked to a solid support by means of a link between said nucleophilic carbene and said solid support.
27. A catalytic complex of the formula:
wherein M is Os or Ru;
in which carbon atom C is bonded to up to two groups R and R 1 ;
R and R 1 are independently selected from the group consisting of hydrogen, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 2 -C 20 alkoxycarbonyl, aryl, C 1 -C 20 carboxylate, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy C 2 -C 20 alkynyloxy, aryloxy, C 1 -C 20 alkylthio, C 1 -C 20 alkylsulfonyl, and C 1 -C 20 alkylsulfinyl each R and R 1 optionally being substituted with C 1 -C 5 alkyl, halogen, C 1 -C 10 alkoxy, or with a phenyl group substituted with halogen, C 1 -C 5 alkyl or C 1 -C 5 alkoxy, or with a functional group;
X and X 1 are independently selected from the group consisting of anionic ligands;
L is selected from the group consisting of phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, ether, amine, amide, sulfoxide, carbonyl, nitrosyl, pyridine and thioether; and
L 1 is of the formula
wherein Y and Y′ are each independently an aryl group substituted with halogen, C 1 -C 5 alkyl, or C 1 -C 5 alkoxy, or with a phenyl group substituted with halogen, C 1 -C 5 alkyl or C 1 -C 5 alkoxy; and
Z and Z 1 are independently selected from the group consisting of hydrogen, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 2 -C 20 alkoxycarbonyl, aryl, C 1 -C 20 carboxylate, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, and aryloxy, each Z and Z 1 optionally being substituted with C 1 -C 5 alkyl, halogen, C 1 -C 5 alkoxy, or with a phenyl group substituted with halogen, C 1 -C 5 alkyl or C 1 -C 5 alkoxy.
28. The catalytic complex according to claim 1 , wherein L is —P(cyclohexyl) 3 , —P(cyclopentyl) 3 or —PPh 3 and L 1 is
29. The method according to claim 11 , wherein the catalytic complex has the formula:
30. The method according to claim 11 , wherein L is —P(cyclohexyl) 3 , —P(cyclopentyl) 3 or —PPh 3 and L 1 is
31. The method according to claim 11 , wherein the catalytic complex has the formula:
32. The method according to claim 31 , wherein L is —P(cyclohexyl) 3 , —P(cyclopentyl) 3 , or —PPh 3 and L 1 is
33. A catalytic complex according to claim 4 , wherein Y and Y 1 are both 2,4,6-trimethylphenyl and Z and Z 1 are both hydrogen.
34. A catalytic complex according to claim 4 , wherein Y and Y 1 are both 2,6-diisopropylphenyl and Z and Z 1 are both hydrogen.
35. A catalytic complex according to claim 6 , wherein Y and Y 1 are both 2,4,6-trimethylphenyl and Z and Z 1 are both hydrogen.
36. The catalytic complex according to claim 6 , wherein Y and Y 1 are both 2,6-diisopropylphenyl and Z and Z 1 are both hydrogen.
37. The method according to claim 12 , wherein Y and Y 1 are both 2,4,6-trimethylphenyl and Z and Z 1 are both hydrogen.
38. The method according to claim 24 , wherein Y and Y 1 are both 2,6-diisopropylphenyl and Z and Z 1 are both hydrogen.
39. The method according to claim 14 , wherein Y and Y 1 are both 2,4,6-trimethylphenyl and Z and Z 1 are both hydrogen.
40. The method according to claim 14 , wherein Y and Y 1 are both 2,6-diisopropylphenyl and Z and Z 1 are both hydrogen.
41. A catalytic complex according to claim 4 , wherein said nucleophilic carbene is of the formula:
42. A catalytic complex according to claim 6 , wherein said nucleophilic carbene is of the formula:
43. The method of claim 12 , wherein the nucleophilic carbene has the formula:
44. The method of claim 14 , wherein the nucleophilic carbene has the formula:
45. A catalytic complex of the formula:
wherein
L is selected from the group consisting of phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, ether, amine, amide, sulfoxide, carbonyl, nitrosyl, pyridine and thioether; and
L 1 is a nucleophilic carbene, wherein L 1 is of the formula
wherein Y and Y 1 are each independently an aryl group substituted with halogen, C 1 -C 5 alkyl, or C 1 -C 5 alkoxy, or with a phenyl group substituted with halogen, C 1 -C 5 alkyl or C 1 -C 5 alkoxy; and
Z and Z 1 are independently selected from the group consisting of hydrogen, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 -alkynyl, C 21 -C 20 alkoxycarbonyl, aryl, C 1 -C 20 carboxylate, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, and aryloxy, each Z and Z 1 optionally being substituted with C 1 -C 5 alkyl, halogen, C 1 -C 5 alkoxy, or with a phenyl group substituted with halogen, C 1 -C 5 alkyl or C 1 -C 5 alkoxy.
46. The catalytic complex of claim 45 , wherein L 1 is
47. A catalytic complex of the formula:
wherein
L is selected from the group consisting of phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, ether, amine, amide, sulfoxide, carbonyl, nitrosyl, pyridine and thioether; and
L 1 is a nucleophilic carbene, wherein L 1 is of the formula
wherein Y and Y 1 are each independently an aryl group substituted with halogen, C 1 -C 5 alkyl, or C 1 -C 5 alkoxy, or with a phenyl group substituted with halogen, C 1 -C 5 alkyl or C 1 -C 5 alkoxy; and
Z and Z 1 are independently selected from the group consisting of hydrogen, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 2 -C 20 alkoxycarbonyl, aryl, C 1 -C 20 carboxylate, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, and aryloxy, each Z and Z 1 optionally being substituted with C 1 -C 5 alkyl, halogen, C 1 -C 5 alkoxy, or with a phenyl group substituted with halogen, C 1 -C 5 alkyl or C 1 -C 5 alkoxy.
48. The catalytic complex of claim 47 , wherein L 1 is
49. The method of claim 11 , wherein the diene is a diterminal diene.
50. The method of claim 13 , wherein the diene is a diterminal diene.
51. The catalytic complex according to claim 4 , wherein the nucleophilic carbene is of the formula:
52. The catalytic complex according to claim 51 , wherein the nucleophilic carbene is of the formula:
53. The catalytic complex according to claim 6 , wherein the nucleophilic carbene is of the formula
54. The catalytic complex according to claim 53 , wherein the nucleophilic carbene is of the formula:
55. The method according to claim 12 , wherein the nucleophilic carbene is of the formula:
56. The method according to claim 55 , wherein the nucleophilic carbene is of the formula:
57. The method according to claim 14 , wherein the nucleophilic carbene is of the formula:
58. The method according to claim 57 , wherein the nucleophilic carbene is of the formula:
59. The catalytic complex according to claim 27 , wherein L 1 is of the formula:
60. The catalytic complex according to claim 1 , wherein L is —P(cyclohexyl) 3 , —P(cyclopentyl) 3 , or —PPh 3 and L 1 is of the formula:
61. The catalytic complex according to claim 41 , wherein the nucleophilic carbene is of the formula:
62. The catalytic complex according to claim 42 , wherein the nucleophilic carbene is of the formula
63. The method according to claim 43 , wherein the nucleophilic carbene is of the formula:
64. The method according to claim 44 , wherein the nucleophilic carbene is of the formula:
65. A catalytic complex of the formula:
wherein M is Os or Ru;
R and Z 1 are independently selected from the group consisting of hydrogen, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 2 -C 20 alkoxycarbonyl, aryl, C 1 -C 20 carboxylate, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, aryloxy, C 1 -C 20 alkylthio, C 1 -C 20 alkylsulfonyl, and C 1 -C 20 alkylsulfinyl, each R and R 1 optionally being substituted with C 1 -C 5 alkyl, halogen, C 1 -C 10 alkoxy, or with a phenyl group substituted with halogen, C 1 -C 5 alkyl or C 1 -C 5 alkoxy, or with a functional group;
X and X 1 are independently selected from the group consisting of anionic ligands;
L is selected from the group consisting of phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, ether, amine, amide, sulfoxide, carbonyl, nitrosyl, pyridine and thioether;
L 1 is a nucleophilic carbene; and
wherein the catalytic complex has one or more further characterization selected from the group consisting of
(1) at least 2 of X, X 1 , L or L 1 are bonded together to form a multidentate ligand;
(2) the complex is linked to a solid support by means of a link between the solid support and the nucleophilic carbene or by means of a link between the solid support and at least one of the anionic ligands;
(3) L 1 has the formula
where Y and Y 1 are independently selected from the group consisting of hydrogen, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 2 -C 20 alkoxycarbonyl, aryl, C 1 -C 20 carboxylate, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, and aryloxy, each Y and Y 1 optionally being substituted with C 1 -C 5 alkyl, halogen, C 1 -C 6 alkoxy, or with a phenyl group substituted with halogen, C 1 -C 5 alkyl or C 1 -C 5 alkoxy; and
Z and Z 1 are independently selected from the group consisting of hydrogen, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 2 -C 20 alkoxycarbonyl, aryl, C 1 -C 20 carboxylate, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, and aryloxy, each Z and Z 1 optionally being substituted with C 1 -C 5 alkyl, halogen, C 1 -C 6 alkoxy, or with a phenyl group substituted with halogen, C 1 -C 5 alkyl or C 1 -C 5 alkoxy; and
(4) any combination of the foregoing characteristics.
66. The catalytic complex of claim 65 , wherein said nucleophilic carbene is of the formula:
wherein
Y and Y 1 are independently selected from the group consisting of hydrogen, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 2 -C 20 alkoxycarbonyl, aryl, C 1 -C 20 carboxylate, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, and aryloxy, each Y and Y 1 optionally being substituted with C 1 -C 5 alkyl, halogen, C 1 -C 6 alkoxy, or with a phenyl group substituted with halogen, C 1 -C 5 alkyl or C 1 -C 5 alkoxyl; and
Z and Z 1 are independently selected from the group consisting of hydrogen, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 2 -C 20 alkoxycarbonyl, aryl, C 1 -C 20 carboxylate, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, and aryloxy, each Z and Z 1 optionally being substituted with C 1 -C 5 alkyl, halogen, C 1 -C 6 alkoxy, or with a phenyl group substituted with halogen, C 1 -C 5 alkyl or C 1 -C 5 alkoxy.
67. The catalytic complex according to claim 66 , wherein the nucleophilic carbene is of the formula:
and wherein the further characterization of the catalytic complex is selected from the group consisting of
(1) at least 2 of X, X 1 , L or L 1 are bonded together to form a multidentate ligand, and
(2) the complex is linked to a solid support by means of a link between the solid support and the nucleophilic carbene or by means of a link between the solid support and at least one of the anionic ligands.
68. The catalytic complex of claim 65 , wherein the further characterization of the catalytic complex is that at least 2 of X, X 1 , L or L 1 are bonded together to form a multidentate ligand.
69. The catalytic complex of claim 65 , wherein the further characterization of the catalytic complex is that the complex is linked to a solid support by means of a link between the solid support and the nucleophilic carbene or by means of a link between the solid support and at least one of the anionic ligands.
70. The catalytic complex of claim 69 , wherein the complex is linked to a solid support by means of a link between at least one of the anionic ligands and the solid support.
71. The catalytic complex according to claim 69 , wherein the complex is linked to a solid support by means of a link between the nucleophilic carbene and said solid support.
72. The catalytic complex of claim 65 , wherein the further characterization of the catalytic complex is that L 1 has the formula
73. A catalytic complex according to claim 66 , wherein Y and Y 1 are both 2,4,6-trimethylphenyl and Z and Z 1 are both hydrogen.
74. A catalytic complex according to claim 66 , wherein Y and Y 1 are both 2,6-diisopropylphenyl and Z and Z 1 are both hydrogen.
75. The catalytic complex according to claim 65 , wherein L is a phosphine.
76. The catalytic complex according to claim 75 , wherein L is —P(cyclohexyl) 3 , —P(cyclopentyl) 3 or —PPh 3 .
77. The catalytic complex according to claim 65 , wherein X and X 1 are independently selected from the group consisting of halide, carboxylate, alkoxy, aryloxy, and alkyl sulfonate.
78. The catalytic complex according to claim 77 , wherein X and X 1 are both chloride.
79. A method for synthesizing a polymer material, the method comprising contacting a monomer composition with the catalytic complex as described in any of claims 1 , 5 , 27 , 28 , 45 , 46 , 47 , 48 , 59 , 60 , 65 , 70 or 71 .
80. The method of claim 79 , wherein the monomer composition comprises a plurality of olefin molecules.
81. The method of claim 79 , wherein the olefin molecules are cyclic olefin molecules.
82. A catalytic complex of the formula:
wherein M is Os or Ru;
R is hydrogen;
R 1 is tert-butyl;
X and X 1 are chloride;
L is selected from the group consisting of phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, ether, amine, amide, sulfoxide, carbonyl nitrosyl, pyridine and thioether; and
L 1 is a nucleophilic carbene of the formula
where Y and Y 1 are independently selected from the group consisting of hydrogen, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 2 -C 20 alkoxycarbonyl, aryl, C 1 -C 20 carboxylate, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, and aryloxy, each Y and Y 1 optionally being substituted with C 1 -C 5 alkyl, halogen, C 1 -C 6 alkoxy, or with a phenyl group substituted with halogen, C 1 -C 5 alkyl or C 1 -C 5 alkoxy; and
Z and Z 1 are independently selected from the group consisting of hydrogen, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 2 -C 20 alkoxycarbonyl, aryl, C 1 -C 20 carboxylate, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, and aryloxy, each Z and Z 1 optionally being substituted with C 1 -C 5 alkyl, halogen, C 1 -C 6 alkoxy, or with a phenyl group substituted with halogen, C 1 -C 5 alkyl or C 1 -C 5 alkoxy.
83. A catalytic complex according to claim 82 , wherein Y and Y 1 are both 2,4,6-trimethylphenyl and Z and Z 1 are both hydrogen.
84. A catalytic complex according to any of claims 1 , 5 , 27 , 28 , or 65 wherein at least one of R and Z 1 is vinyl, phenyl, or hydrogen.
85. A catalytic complex according to claim 84 wherein at least one of R and R 1 is phenyl.
86. A catalytic complex according to any of claims 1 , 5 , or 28 wherein R or R 1 is an aryl group, and a rearrangement of C 1 ═C 2 ═C 3 with said aryl group forms a ring between C 1 and a carbon atom of said aryl group.
87. A catalytic complex according to any of claims 1 , 5 , or 28 wherein R or R 1 is a phenyl group, and a rearrangement of C 1 ═C 2 ═C 3 with said phenyl group forms a ring between C 1 and a carbon atom of said phenyl group.
88. A catalytic complex according to any of claims 1 , 5 , 27 , 28 , or 65 wherein R and R 1 each independently or together are cyclic or polycyclic.
89. A method according to claim 11 or 13 wherein at least one of R and R 1 is vinyl, phenyl, or hydrogen.
90. A method according to claim 89 wherein at least one of R and R 1 is phenyl.
91. A method according to any of claims 11 , 12 , 13 , or 14 wherein R or R 1 is an aryl group, and a rearrangement of C 1 ═C 2 ═C 3 with said aryl group forms a ring between C 1 and a carbon atom of said aryl group.
92. A method according to any of claim 11 , 12 , 13 , or 14 wherein R or R 1 is a phenyl group, and a rearrangement of C 1 ═C 2 ═C 3 with said phenyl group forms a ring between C 1 and a carbon atom of said phenyl group.
93. A method according to claim 11 or 13 wherein R and R 1 each independently or together are cyclic or polycyclic.
94. A catalytic complex according to any of claims 27 , 45 , 47 or 82 wherein L is —P(cyclohexyl) 3 , —P(cyclopentyl) 3 , or —PPh 3 .
95. A catalytic complex according to any of claims 1 , 27 , 45 , 47 , 65 or 82 wherein at least two of X, X 1 , L or L 1 are bonded together to form a multidentate ligand.
96. A method according to claim 11 wherein at least two of X, X 1 , L or L 1 are bonded together to form a multidentate ligand.
97. A catalytic complex according to any of claims 27 , 45 , or 47 wherein Y and Y 1 are each independently an aryl group substituted with halogen, C 1 -C 5 alkyl, or C 1 -C 5 alkoxy groups.
98. A catalytic complex according to any of claims 27 , 45 , or 47 wherein Y and Y 1 are 2,4,6-trimethylphenyl or 2,6-diisopropyl, and Z and Z 1 are hydrogen.
99. A catalytic complex according to claim 87 wherein R and R 1 are phenyl groups.
100. A method according to claim 92 wherein R and R 1 are phenyl groups.