Ruthenium complexes useful for catalyzing metathesis reactions

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

• wherein:
• each of R6 and R7 is independently R, —CN, halogen, —OR, —OC(O)R, —OSiR3, —SR, —S(O)R, —S(O)2R, —NO2, —N(R′)2, —NR′C(O)R, —NR′C(O)OR, —NR′C(O)N(R′)2, —NR′SO2R, —NR′SO2N(R′)2, —NR′OR, —SeR, —SiR3;
• or R6 and R7 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:
• R1 is a carbene of formula 7a
• wherein each R in formula 7a is independently hydrogen, C1-C12 alkyl, C3-C12 cycloalkyl, C2-C12 alkenyl, C6-C14 aryl, C1-C5 perfluoroalkyl, C7-C24 aralkyl, or C6-C14 perfluoroaryl group, which are optionally substituted with at least one C1-C12 alkyl, C1-C12 perfluoroalkyl, C1-C12 alkoxy, C6-C14 aryloxy, or a halogen atom;
• and wherein two R which are separated by the C—CR2—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, C1-C12 alkyl, C3-C12 cycloalkyl, C2-C12 alkenyl, C6-C14 aryl, C1-C5 perfluoroalkyl, C7-C24 aralkyl, or C6-C14 perfluoroaryl group, which are optionally substituted with at least one C1-C12 alkyl, C1-C12 perfluoroalkyl, C1-C12 alkoxy, C6-C14 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 Ry independently has the meaning of C1-C12 alkyl, C1-C12 perfluoroalkyl, C1-C12 alkoxy, C6-C14 aryl, C6-C14 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 Ry independently has the meaning of C1-C12 alkyl, C1-C12 perfluoroalkyl, C1-C12 alkoxy, C6-C14 aryl, C6-C14 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 C1-C12 alkyl, or C3-C12 cycloalkyl, or C2-C12 alkenyl, C6-C14 aryl, C1-C5 perfluoroalkyl, C7-C24 aralkyl, or C6-C14 perfluoroaryl group, which are optionally substituted with at least one C1-C12 alkyl, C1-C12 perfluoroalkyl, C1-C12 alkoxy, C6-C14 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:
• C1-C12 alkyl, C1-C12 perfluoroalkyl, C1-C12 alkoxy, C6-C14 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 Rx 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, —OSiR3, —N(R′)2, —N(R′)3+, —NR′C(O)R, —NR′C(O)OR, —NR′C(O)N(R′)2, —NR′SO2R, —NR′SO2N(R′)2, —NR′OR, —NO2, —SiR3, —PR2, —P(O)R2, —P(O)(OR)2, —SR, —SC(O)R, —S(O)R, —SO2R, —SO3R, —SO2N(R′)2, or —SeR,
• each R′ is independently R, —C(O)R, —C(O)NR2, —C(O)OR, —SO2R, —SO2NR2, —P(O)(OR)2, or —OR;
• each R is independently hydrogen or an optionally substituted group selected from C1-20 aliphatic, C1-20 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;
• R2 is H;
• R3 is hydrogen or an optionally substituted group selected from C1-20 aliphatic, C1-20 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—.