Ruthenium complexes useful for catalyzing metathesis reactions

1. A ruthenium complex having the structure of formula I-c:

wherein:

each of R 6 and R 7 is independently R, —CN, halogen, —OR, —OC(O)R, —OSiR 3 , —SR, —S(O)R, —S(O) 2 R, —NO 2 , —N(R′) 2 , —NR′C(O)R, —NR′C(O)OR, —NR′C(O)N(R′) 2 , —NR′SO 2 R, —NR′SO 2 N(R′) 2 , —NR′OR, —SeR, —SiR 3 ; or R 6 and R 7 are optionally taken together with their intervening atoms to form an optionally substituted 3-10 membered, saturated, partially unsaturated or aryl monocyclic or bicyclic ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur;

or wherein the complex has the structure of formula I-d:

or wherein the complex has the structure of formula I-e:

or wherein the complex has the structure of formula I-f:

wherein in each of formulas I-c to I-f:

R 1 is a carbene of formula 7a

wherein each R in formula 7a is independently hydrogen, C 1 -C 12 alkyl, C 3 -C 12 cycloalkyl, C 2 -C 12 alkenyl, C 6 -C 14 aryl, C 1 -C 5 perfluoroalkyl, C 7 -C 24 aralkyl, or C 6 -C 14 perfluoroaryl group, which are optionally substituted with at least one C 1 -C 12 alkyl, C 1 -C 12 perfluoroalkyl, C 1 -C 12 alkoxy, C 6 -C 14 aryloxy, or a halogen atom; and wherein two R which are separated by the C—CR 2 —C moiety can be combined with to form a cyclic system;

or is a carbene of formula 7b

wherein each R in formula 7b is independently hydrogen, C 1 -C 12 alkyl, C 3 -C 12 cycloalkyl, C 2 -C 12 alkenyl, C 6 -C 14 aryl, C 1 -C 5 perfluoroalkyl, C 7 -C 24 aralkyl, or C 6 -C 14 perfluoroaryl group, which are optionally substituted with at least one C 1 -C 12 alkyl, C 1 -C 12 perfluoroalkyl, C 1 -C 12 alkoxy, C 6 -C 14 aryloxy, or a halogen atom; and wherein n is 1, 2 or 3;

or is a carbene of formula 7c

wherein in formula 7c m is an integer of from 0 to 4, and each R y independently has the meaning of C 1 -C 12 alkyl, C 1 -C 12 perfluoroalkyl, C 1 -C 12 alkoxy, C 6 -C 14 aryl, C 6 -C 14 aryloxy, or halogen;

or is a carbene of formula 7d

wherein in formula 7d m is an integer of from 0 to 4, and each R y independently has the meaning of C 1 -C 12 alkyl, C 1 -C 12 perfluoroalkyl, C 1 -C 12 alkoxy, C 6 -C 14 aryl, C 6 -C 14 aryloxy, or halogen;

or is a carbene of formula 7e

or is a carbene of formula 7f

or is a carbene of formula 7g or 7h

or is a carbene of formula 7i

or is a carbene of formula 7k

wherein each R in formulae 7c to 7i is independently hydrogen or C 1 -C 12 alkyl, or C 3 -C 12 cycloalkyl, or C 2 -C 12 alkenyl, C 6 -C 14 aryl, C 1 -C 5 perfluoroalkyl, C 7 -C 24 aralkyl, or C 6 -C 14 perfluoroaryl group, which are optionally substituted with at least one C 1 -C 12 alkyl, C 1 -C 12 perfluoroalkyl, C 1 -C 12 alkoxy, C 6 -C 14 aryloxy, or a halogen atom;

wherein Ar as defined in formulae 7a to 7k is aryl, optionally substituted with one or more groups selected from: C 1 -C 12 alkyl, C 1 -C 12 perfluoroalkyl, C 1 -C 12 alkoxy, C 6 -C 14 aryloxy, or halogen;

r is 1;

X and Y are —S—;

Ring A is an optionally substituted ring selected from phenyl, an 8-10 membered bicyclic aryl ring, a 5-6 membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or an 8-10 membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur;

each R x is independently halogen, R, —CN, —C(O)N(R′) 2 , —C(O)R, —C(O)OR, —OR, —OC(O)R, —OC(O)OR, —OC(O)N(R′) 2 , —OSiR 3 , —N(R′) 2 , —N(R′) 3 + , —NR′C(O)R, —NR′C(O)OR, —NR′C(O)N(R′) 2 , —NR′SO 2 R, —NR′SO 2 N(R′) 2 , —NR′OR, —NO 2 , —SiR 3 , —PR 2 , —P(O)R 2 , —P(O)(OR) 2 , —SR, —SC(O)R, —S(O)R, —SO 2 R, —SO 3 R, —SO 2 N(R′) 2 , or —SeR,

each R′ is independently R, —C(O)R, —C(O)NR 2 , —C(O)OR, —SO 2 R, —SO 2 NR 2 , —P(O)(OR) 2 , or —OR;

each R is independently hydrogen or an optionally substituted group selected from C 1-20 aliphatic, C 1-20 heteroaliphatic, phenyl, a 3-7 membered saturated or partially unsaturated carbocyclic ring, an 8-10 membered bicyclic saturated, partially unsaturated or aryl ring, a 5-6 membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 3-7 membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 7-10 membered bicyclic saturated or partially unsaturated heterocyclic ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or an 8-10 membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or:

two R groups are optionally taken together with their intervening atoms to form an optionally substituted 3-10 membered, saturated, partially unsaturated, or aryl ring having, in addition to the intervening atoms, 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur;

m is 0-6;

R 2 is H;

R 3 is hydrogen or an optionally substituted group selected from C 1-20 aliphatic, C 1-20 heteroaliphatic, phenyl, a 3-7 membered saturated or partially unsaturated carbocyclic ring, a 5-6 membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or a 3-7 membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and

Z is —O—.

2. The complex of claim 1 , wherein the complex has the structure of formula I-g:

3. The complex of claim 1 , wherein the carbene of formula 7a is of formula 7a′

wherein R 12 , R 13 , R 14 , and R 15 in formula 7a are each independently hydrogen, C 1 -C 12 alkyl, C 3 -C 12 cycloalkyl, C 2 -C 12 alkenyl, C 6 -C 14 aryl, C 1 -C 5 perfluoroalkyl, C 7 -C 24 aralkyl, or C 6 -C 14 perfluoroaryl group, which are optionally substituted with at least one C 1 -C 12 alkyl, C 1 -C 12 perfluoroalkyl, C 1 -C 12 alkoxy, C 6 -C 14 aryloxy, or a halogen atom; and wherein R 12 and/or R 13 can be combined with R 14 and/or R 15 to form a cyclic system; or

wherein the carbene of formula 7b is of formula 7b′:

wherein R 16 , R 17 and R 18 in formula 7b′ are each independently hydrogen or C 1 -C 12 alkyl, or C 3 -C 12 cycloalkyl, or C 2 -C 12 alkenyl, C 6 -C 14 aryl, C 1 -C 5 perfluoroalkyl, C 7 -C 24 aralkyl, or C 6 -C 14 perfluoroaryl group, which are optionally substituted with at least one C 1 -C 12 alkyl, C 1 -C 12 perfluoroalkyl, C 1 -C 12 alkoxy, C 6 -C 14 aryloxy, or a halogen atom.

4. The complex of claim 1 , wherein the complex is

5. The complex of claim 1 , wherein the complex is immobilized on a solid support.

6. A method of catalysing a metathesis reaction, comprising: metathesizing one or more olefins in the presence of a complex as defined in claim 1 .

7. The method of claim 6 , wherein more than 80% of the olefins formed in the catalysed metathesis reaction are Z-olefins.

8. The complex of claim 1 , wherein Ar as defined in formulae 7a to 7k is phenyl, optionally substituted with one or more groups selected from: C 1 -C 12 alkyl, C 1 -C 12 perfluoroalkyl, C 1 -C 12 alkoxy, C 6 -C 14 aryloxy, or halogen.

9. The complex of claim 1 , wherein R in formula 7b are each independently hydrogen, C 1 -C 12 alkyl, or C 3 -C 12 cycloalkyl.

10. The complex of claim 3 , wherein R 16 , R 17 and R 18 in formula 7b′ are each independently hydrogen, C 1 -C 12 alkyl, or C 3 -C 12 cycloalkyl.

11. The complex of claim 1 , wherein each R in formulae 7c to 7i is hydrogen, C 1 -C 12 alkyl, or C 3 -C 12 cycloalkyl.

12. The complex of claim 1 , wherein the carbene of formula 7c is a carbene of formula 7c′

13. The complex of claim 1 , wherein the carbene of formula 7d is a carbene of formula 7d′

14. The complex of claim 1 , wherein each R in formula 7b is independently hydrogen, C 1 -C 12 alkyl, or C 3 -C 12 cycloalkyl, optionally substituted with at least one C 1 -C 12 alkyl, C 1 -C 12 perfluoroalkyl, C 1 -C 12 alkoxy, C 6 -C 14 aryloxy, or a halogen atom.

15. The complex of claim 1 , wherein Ar as defined in formulae 7a to 7k is phenyl, optionally substituted with one or more groups selected from: C 1 -C 12 alkyl, C 1 -C 12 perfluoroalkyl, C 1 -C 12 alkoxy, C 6 -C 14 aryloxy, or halogen.