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 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, and aryl, each R and R 1 optionally being substituted with C 1 -C 5 alkyl, halogen, C 1 - C 10 alkoxy, or 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 carbine;
Ar is an η 6 —C 6 H 6 N or an alkyl substituted C 6 H 6 ring system; and
A 31 is an inorganic anion or an organic anion.
2. A method of performing ring closing metathesis, said method comprising contacting a diene with a catalytic complex of claim 1 under conditions appropriate, and for a time sufficient to produce a cyclic alkene.
3. A method of making catalytic complexes of claim 1 where both of C 1 and C 2 are present, said method comprising combining a precursor species of the formula
with a terminal acetylene, which can be substituted at the γ-position with alkyl or aryl groups, or optionally further substituted with alkyl or alkoxy groups of from 1 to 10 carbon atoms, or aryl groups, or functional groups of hydroxyl, thiol, thioether, ketone, aldehyde, ester, amide, amine, imine, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, and halogen,
and in the precursor species
M is selected from the group consisting of Os and Ru;
X and X 1 are anionic ligands;
L is a nucleophilic carbene; and
Ar is an η 6 —C 6 H 6 N or an alkyl substituted C 6 H 6 ring system.
4. A method as in claim 3 wherein the precursor species is formed from a dimer of the formula [ArMXX 1 ] 2 by exposing the dimer to a nucleophilic carbene in a suitable solvent.
5. A catalytic complex according to claim 1 , wherein X is a halide.
6. A catalytic complex according to claim 5 , wherein L is a nucleophilic carbene 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 C 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.
7. A catalytic complex according to claim 6 , wherein the 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 C 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.
8. A catalytic complex according to claim 7 , wherein Y and Y 1 are both 2,4,6-trimethylphenyl or both 2,6-diisopropylphenyl; and Z and Z 1 are both hydrogen.
9. A catalytic complex according to claim 1 , wherein both of C 1 and C 2 are present; M is Ru; X is chloride; Ar is p-cymene; R and R 1 are both phenyl; A − is PF 6 − ; and L is a nucleophilic carbene 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 C 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.
10. A catalytic complex according to claim 9 , wherein the 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 C 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.
11. A catalytic complex according to claim 10 , wherein Y and Y 1 are both 2,4,6-trimethylphenyl or both 2,6-diisopropylphenyl; and Z and Z 1 are both hydrogen.
12. A method according to claim 2 , wherein the cyclic alkene is disubstituted, trisubstituted, or tetrasubstituted.
13. A method according to claim 2 , wherein both of C 1 and C 2 are present; M is Ru; X is chloride; Ar is p-cymene; R and R 1 are both phenyl; A 31 is PF 6 31 ; and L is a nucleophilic carbene 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 C 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.
14. A method according to claim 13 , wherein the 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 C 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. A method according to claim 14 , wherein Y and Y 1 are both 2,4,6-trimethylphenyl or both 2,6-diisopropylphenyl; and Z and Z 1 are both hydrogen.
16. A method according to claim 3 , wherein the terminal acetylene is substituted at the γ-position with alkyl or aryl groups, or optionally further substituted with alkyl or alkoxy groups of from 1 to 10 carbon atoms, or aryl groups, or hydroxyl.
17. A method according to claim 16 , wherein in the precursor species X and X 1 are both a halide.
18. A method according to claim 17 , wherein in the precursor species L is a nucleophilic carbene 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 C 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.
19. A method according to claim 18 , wherein the 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 C 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.
20. A method according to claim 19 , wherein Y and Y 1 are both 2,4,6-trimethylphenyl or both 2,6-diisopropylphenyl; and Z and Z 1 are both hydrogen.
21. A method according to claim 4 , wherein the dimer of the formula [ArMXX 1 ] 2 is [(p-cymene)-RuCl 2 ] 2 .
22. A method according to claim 2 , wherein the catalytic complex is of claim 6 .