Isoselective polymerization of epoxides

A bimetallic complex of formula I selected from the group consisting of formulas I-a, I-b, and I-c:

• wherein:
• M is a metal atom;
• X is a nucleophile;
• n is an integer from 0 to 2, inclusive
• each occurrence of L1, L2, Y1, and Y2 is independently —O—, —P(R′)2—, ═NR′—, or —N(R′)2—;
• each occurrence of
• is an optionally substituted moiety selected from the group consisting of C2-12 aliphatic, C7-12 arylalkyl;
• 6-10-membered aryl;
• 5-10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur;
• and 4-7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;
• each occurrence of
• is an optionally substituted moiety selected from the group consisting of C7-12 arylalkyl;
• 6-10-membered aryl;
• and 5-10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur;
• represents a single bond directly attached to an aryl or heteroaryl ring of each
• each occurrence of R′ is hydrogen or an optionally substituted moiety selected from the group consisting of a C3-C14 carbocycle, a C6-C10 aryl group, a C3-C14 heterocycle, and a C5-C10 heteroaryl group;
• or an optionally substituted C2-20 aliphatic group, wherein one or more methylene units are optionally and independently replaced by —NRy—, —N(Ry)C(O)—, —C(O)N(Ry)—, —OC(O)N(Ry)—, —N(Ry)C(O)O—, —OC(O)O—, —O—, —C(O)—, —OC(O)', —C(O)O—, —S—, —SO—, —SO2—, —C(═S)—, —C(═NRy)—, —C(═NORy)— or —N═N—;
• or
• two R′ are taken together with their intervening atoms to form a monocyclic or bicyclic 5-12-membered ring;
• wherein a substituent may comprise one or more organic cations;
• each occurrence of Q is an optionally substituted moiety selected from the group consisting of a C3-C14 carbocycle, a C6-C10 aryl group, a C3-C14 heterocycle, and a C5-C10 heteroaryl group;
• or an optionally substituted C2-20 aliphatic group, wherein one or more methylene units are optionally and independently replaced by —NRy—, —N(Ry)C(O)—, —C(O)N(Ry)—, —OC(O)N(Ry)—, —N(Ry)C(O)O—, —OC(O)O—, —O—, —C(O)—, —OC(O)—, —C(O)O—, —S—, —SO—, —SO2—, —C(═S)—, —C(═NRy)—, —C(═NORy)—or —N═N—;
• each occurrence of Ry is independently hydrogen or an optionally substituted C1-6 aliphatic group;
• each occurrence of R1 and R2 is independently hydrogen, halogen, —NO2, —CN, —SRy, —S(O)Ry, —S(O)2Ry, —NRyC(O)Ry, —OC(O)Ry, —CO2Ry, —NCO, —N3, —ORy, —OC(O)N(Ry)2,—N(Ry)2,, —NRyC(O)Ry, —NRyC(O)ORy;
• or an optionally substituted group selected from the group consisting of C1-12 aliphatic;
• C1-12 heteroaliphatic having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;
• 6-10-membered aryl;
• 5-10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur;
• and 4-7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;
• or
• R1 and R2 are taken together with their intervening atoms to form an optionally substituted 4-14-membered carbocycle, an optionally substituted 4-14-membered heterocycle, an optionally substituted 6-10-membered aryl group or an optionally substituted 5-10-membered heteroaryl group having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur ring;
• and
• each occurrence of R3 and R4 is independently hydrogen, halogen, —NO2, —CN, —SRy, —S(O)Ry, —S(O)2Ry, —NRyC(O)Ry, —OC(O)Ry, —CO2Ry, —NCO, —N3, —ORy, —OC(O)N(Ry)2 —N(Ry)2, —NRyC(O)R, —NRyC(O)ORy;
• or an optionally substituted group selected from the group consisting of C1-12 aliphatic;
• C1-12 heteroaliphatic having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;
• 6-10-membered aryl;
• 5-10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur;
• and 4-7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;
• each occurrence of R5, R5a, and R5b is independently hydrogen, halogen, —NO2, —CN, —SRy, —S(O)Ry, —S(O)2Ry, —NRyC (O)Ry, —OC(O)Ry, —CO2Ry, —NCO, —N3, —ORy, —OC(O)N(Ry)2,—N(Ry)2, —NRyC(O)Ry, —NRyC(O)ORy;
• or an optionally substituted group selected from the group consisting of C1-12 aliphatic;
• C1-12 heteroaliphatic having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;
• 6-10-membered aryl;
• 5-10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur;
• and 4-7-membered heterocyclic having 1-2heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;
• wherein adjacent R5, R5a, or R5b groups can be taken together to form an optionally substituted saturated, partially unsaturated, or aromatic 5- to 12-membered ring containing 0 to 4 heteroatoms;
• each occurrence of R5, R6, R7, R8, and R9 is independently hydrogen, halogen, —NO2, —CN, —SRy, —S(O)Ry, —S(O)2Ry, —NRyC(O)Ry, —OC(O)Ry, —CO2Ry, —NCO, —N3, —ORy, —OC(O)N(Ry)2, —N(Ry)2, —NRyC(O)Ry, —NRyC(O)ORy;
• or an optionally substituted group selected from the group consisting of C1-12 aliphatic;
• C1-12 heteroaliphatic having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;
• 6-10-membered aryl;
• 5-10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur;
• and 4-7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;
• wherein adjacent R6, R7, R8, or R9 groups can be taken together to form an optionally substituted saturated, partially unsaturated, or aromatic 5- to 12-membered ring containing 0 to 4 heteroatoms;
• and
• each occurrence of Ry is independently hydrogen or an optionally substituted C1-6 aliphatic group.