Catalysts and methods for polymer synthesis

Abstract

The present invention provides unimolecular metal complexes having increased activity in the copolymerization of carbon dioxide and epoxides. Also provided are methods of using such metal complexes in the synthesis of polymers. According to one aspect, the present invention provides metal complexes comprising an activating species with co-catalytic activity tethered to a multidentate ligand that is coordinated to the active metal center of the complex.

Claims

1. A method for the synthesis of aliphatic polycarbonates comprising the step of contacting an epoxide and carbon dioxide with a metal complex comprising a metal atom coordinated with a salen ligand, the salen ligand comprising two halves, each half coordinated to the metal atom via an imine and an oxygen atom, wherein the metal complex is characterized in that one of the two halves of the salen ligand has two or more cationic activating functional groups tethered to it and the other half has no tethered cationic activating functional groups, wherein the metal complex is of formula IVa: ##STR00266## wherein, M is a metal atom; X is a nucleophile capable of ring opening an epoxide; k is an integer from 0-2 inclusive; R represents one or more substituents optionally present on the phenyl rings and each R is independently selected from the group consisting of: halogen, NO.sub.2, CN, SR.sup.y, S(O)R.sup.y, S(O).sub.2R.sup.y, NR.sup.yC(O)R.sup.y, OC(O)R.sup.y, CO.sub.2R.sup.y, NCO, N.sub.3, OR.sup.7, OC(O)N(R.sup.y).sub.2, N(R.sup.y).sub.2, NR.sup.yC(O)R.sup.y, NR.sup.yC(O)OR.sup.y; or an optionally substituted radical selected from the group consisting of C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur, where two or more adjacent R 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; R.sup.y is H, or an optionally substituted radical selected from the group consisting of C.sub.1-6 aliphatic, 3- to 7-membered heterocyclic, phenyl, and 8- to 10-membered aryl; R.sup.4a, R.sup.6a, and R.sup.7a are each independently a (Z).sub.m group, hydrogen, halogen, OR, NR.sub.2, SR, CN, NO.sub.2, SO.sub.2R, SOR, SO.sub.2NR.sub.2; CNO, NRSO.sub.2R, NCO, N.sub.3, SiR.sub.3; or an optionally substituted radical selected from the group consisting of C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur, wherein R at each occurrence is independently hydrogen, an optionally substituted radical selected the group consisting of acyl; C.sub.1-6 aliphatic; C.sub.1-6 heteroaliphatic; carbamoyl; arylalkyl; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; an oxygen protecting group; and a nitrogen protecting group, where two R groups on the same nitrogen atom can optionally be taken together to form an optionally substituted 3- to 7-membered ring; wherein R.sup.6a and R.sup.7a can be taken together with intervening atoms to form one or more optionally substituted rings; R.sup.7 is hydrogen, a hydroxyl protecting group, or an optionally substituted radical selected from the group consisting of C.sub.1-20 acyl; C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; represents an optionally substituted moiety linking the two nitrogen atoms of the diamine portion of the salen ligand, where is selected from the group consisting of phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an optionally substituted C.sub.2-20 aliphatic group, wherein one or more methylene units are optionally and independently replaced by NR.sup.y, N(R.sup.y)C(O), C(O)N(R.sup.y), OC(O)N(R.sup.y), N(R.sup.y)C(O)O, OC(O)O, O, C(O), OC(O), C(O)O, S, SO, SO.sub.2, C(S), C(NR.sup.y), C(NOR.sup.y) or NN; and (Z).sub.m represents one or more activating moieties, where is a covalent linker containing one or more atoms selected from the group consisting of C, O, N, S, and Si; Z is a cationic functional group and each m is independently an integer from 1 to 4 indicating the number of individual cationic functional groups present in each activating moiety; wherein a total of at least two cationic functional groups (Z) are present, wherein each cationic activating functional group (Z) is independently a phosphorus-containing functional group or ##STR00267## where X.sup. is any anion; and R.sup.11, R.sup.12, and R.sup.13 are each independently C.sub.1-C.sub.20 alkyl; C.sub.1-C.sub.20 alkyl having one or more functional moieties selected from the group consisting of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; C.sub.2-C.sub.20 alkenyl; C.sub.2-C.sub.20 alkenyl having one or more functional moieties selected from the group consisting of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; C.sub.7-C.sub.20 alkylaryl; C.sub.7-C.sub.20 alkylaryl having one or more functional moieties selected from the group consisting of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; C.sub.7-C.sub.20 arylalkyl; C.sub.7-C.sub.20 arylalkyl having one or more functional moieties selected from the group consisting of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; or a metalloid radical of group XIV metal substituted by hydrocarbyl, two of R.sup.11 and R.sup.13 being optionally fused together to form a bridged structure.

2. The method of claim 1, wherein the cationic activating functional groups are each ##STR00268##

3. The method of claim 1, wherein the half of the ligand having no tethered cationic activating functional groups is derived from salicylaldehyde optionally substituted with one or more aliphatic groups.

4. The method of claim 1, wherein the metal atom is selected from the group consisting of Cr, Mn, V, Fe, Co, Mo, W, Ru, Al, and Ni.

5. The method of claim 1, wherein the metal atom is Co.

6. The method of claim 1, wherein each moiety independently contains 1-30 atoms including at least one carbon atom, and optionally one or more atoms selected from the group consisting of N, O, S, Si, B, and P.

7. The method of claim 6, wherein each moiety is independently a C.sub.2-30 aliphatic group wherein one or more methylene units are optionally and independently replaced by NR.sup.y, N(R.sup.y)C(O), C(O)N(R.sup.y), O, C(O), OC(O), C(O)O, S, Si(R.sup.y).sub.2, SO, SO.sub.2, C(S), C(NR.sup.y), or NN, where each occurrence of R.sup.y is independently H, or an optionally substituted radical selected from the group consisting of C.sub.1-6 aliphatic, 3- to 7-membered heterocyclic, phenyl, and 8- to 10-membered aryl.

8. The method of claim 1, wherein each moiety is independently selected from the group consisting of: ##STR00269## ##STR00270## where * represents the site of attachment to the ligand, and each # represents a site of attachment of an activating functional group.

9. The method of claim 1, wherein there is one (Z).sub.m group present and it is selected from the group consisting of: ##STR00271##

10. The method of claim 9, wherein the (Z).sub.m moiety is selected from the group consisting of: ##STR00272##

11. The method of claim 1, wherein there is one (Z).sub.m group present and it is selected from the group consisting of: ##STR00273## wherein s is 0-6, t is 1-4, * represents the site of attachment to the ligand, and each # represents a site of attachment of an activating functional group.

12. The method of claim 11, wherein the (Z).sub.m moiety is selected from the group consisting of: ##STR00274##

13. The method of claim 1, wherein each R, when present, is independently C.sub.1-20 aliphatic.

14. The method of claim 1, wherein each R.sup.4a, R.sup.6a, and R.sup.7a is independently selected from the group consisting of: H, optionally substituted C.sub.1-20 aliphatic, optionally substituted phenyl, and optionally substituted 8- to 10-membered aryl.

15. The method of claim 14, wherein each R.sup.4a, and R.sup.6a is H.

16. The method of claim 15, wherein R.sup.7a is R.sup.7a C.sub.1-20 aliphatic.

17. The method of claim 1, wherein one salicylaldehyde-derived portion of the metal complex is selected from the group consisting of: ##STR00275## ##STR00276##

18. The method of claim 1, wherein the half of the salen ligand having two or more tethered cationic activating groups comprises: ##STR00277##

19. The method of claim 1, wherein one or more Z groups is a cationic moiety independently selected from the group consisting of: ##STR00278## where X.sup. is any anion; R.sup.11, R.sup.12, R.sup.13, R.sup.21, R.sup.22, R.sup.23, R.sup.24 and R.sup.25 are each independently C.sub.1-C.sub.20 alkyl; C.sub.1-C.sub.20 alkyl having one or more functional moieties selected from the group consisting of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; C.sub.2-C.sub.20 alkenyl; C.sub.2-C.sub.20 alkenyl having one or more functional moieties selected from the group consisting of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; C.sub.7-C.sub.20 alkylaryl; C.sub.7-C.sub.20 alkylaryl having one or more functional moieties selected from the group consisting of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; C.sub.7-C.sub.20 arylalkyl; C.sub.7-C.sub.20 arylalkyl having one or more functional moieties selected from the group consisting of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; or a metalloid radical of group XIV metal substituted by hydrocarbyl, two of R.sup.11, R.sup.12 and R.sup.13, or two of R.sup.21, R.sup.22, R.sup.23, R.sup.24 and R.sup.25 being optionally fused together to form a bridged structure.

20. The method of claim 19, wherein each Z is ##STR00279##

21. The method of claim 20, wherein each R.sup.1, R.sup.2, and R.sup.3 group is an alkyl group.

22. The method of claim 20, wherein each R.sup.1, R.sup.2, and R.sup.3 group is independently a C.sub.1-C.sub.20 straight chain, branched, or cyclic alkyl group.

23. The method of claim 20, wherein each R.sup.1, R.sup.2, and R.sup.3 group is independently a C.sub.1-C.sub.12 straight or branched alkyl group.

24. The method of claim 20, wherein each R.sup.1, R.sup.2, and R.sup.3 group is independently a C.sub.1-C.sub.8 straight or branched alkyl group.

25. The method of claim 20, wherein each R.sup.1, R.sup.2, and R.sup.3 group is independently selected from the group consisting of: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, and n-hexyl.

26. The method of claim 20, wherein each R.sup.1, R.sup.2, and R.sup.3 group is n-butyl.

27. The method of claim 1, wherein the epoxide is selected from the group consisting of: ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, 1,2 octene oxide, 3-vinyl cyclohexene oxide, epichlorohydrin and mixtures of any two or more of these.

28. The method of claim 27, wherein the epoxide is propylene oxide.

29. A metal complex of formula IVa: ##STR00280## wherein, M is a metal atom; X is a nucleophile capable of ring opening an epoxide; k is an integer from 0-2 inclusive; R represents one or more substituents optionally present on the phenyl rings and each R is independently selected from the group consisting of: halogen, NO.sub.2, CN, SR.sup.y, S(O)R.sup.y, S(O).sub.2R.sup.y, NR.sup.yC(O)R.sup.y, OC(O)R.sup.y, CO.sub.2R.sup.y, NCO, N.sub.3, OR.sup.7, OC(O)N(R.sup.y).sub.2, N(R.sup.y).sub.2, NR.sup.yC(O)R.sup.y, NR.sup.yC(O)OR.sup.y; or an optionally substituted radical selected from the group consisting of C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur, where two or more adjacent R 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; R.sup.y is H, or an optionally substituted radical selected from the group consisting of C.sub.1-6 aliphatic, 3- to 7-membered heterocyclic, phenyl, and 8- to 10-membered aryl; R.sup.4a, R.sup.6a, and R.sup.7a are each independently a (Z).sub.m group, hydrogen, halogen, OR, NR.sub.2, SR, CN, NO.sub.2, SO.sub.2R, SOR, SO.sub.2NR.sub.2; CNO, NRSO.sub.2R, NCO, N.sub.3, SiR.sub.3; or an optionally substituted radical selected from the group consisting of C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur, wherein R at each occurrence is independently hydrogen, an optionally substituted radical selected the group consisting of acyl; C.sub.1-6 aliphatic; C.sub.1-6 heteroaliphatic; carbamoyl; arylalkyl; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; an oxygen protecting group; and a nitrogen protecting group, where two R groups on the same nitrogen atom can optionally be taken together to form an optionally substituted 3- to 7-membered ring; wherein R.sup.6a and R.sup.7a can be taken together with intervening atoms to form one or more optionally substituted rings; R.sup.7 is hydrogen, a hydroxyl protecting group, or an optionally substituted radical selected from the group consisting of C.sub.1-20 acyl; C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; represents is an optionally substituted moiety linking the two nitrogen atoms of the diamine portion of the salen ligand, where is selected from the group consisting of phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an optionally substituted C.sub.2-20 aliphatic group, wherein one or more methylene units are optionally and independently replaced by NR.sup.y, N(R.sup.y)C(O), C(O)N(R.sup.y), OC(O)N(R.sup.y), N(R.sup.y)C(O)O, OC(O)O, O, C(O), OC(O), C(O)O, S, SO, SO.sub.2, C(S), C(NR.sup.y), C(NOR.sup.y) or NN; and (Z).sub.m represents one or more activating moieties, where is a covalent linker containing one or more atoms selected from the group consisting of C, O, N, S, and Si; Z is a cationic functional group and each m is independently an integer from 1 to 4 indicating the number of individual cationic functional groups present in each activating moiety; wherein a total of at least two cationic functional groups (Z) are present, wherein each cationic activating functional group (Z) is independently a phosphorus-containing functional group or ##STR00281## where X.sup. is any anion; and R.sup.11, R.sup.12, and R.sup.13 are each independently C.sub.1-C.sub.20 alkyl, C.sub.1-C.sub.20 alkyl having one or more functional moieties selected from the group consisting of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; C.sub.2-C.sub.20 alkenyl; C.sub.2-C.sub.20 alkenyl having one or more functional moieties selected from the group consisting of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; C.sub.7-C.sub.20 alkylaryl; C.sub.7-C.sub.20 alkylaryl having one or more functional moieties selected from the group consisting of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; C.sub.7-C.sub.20 arylalkyl; C.sub.7-C.sub.20 arylalkyl having one or more functional moieties selected from the group consisting of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; or a metalloid radical of group XIV metal substituted by hydrocarbyl, two of R.sup.11, R.sup.12 and R.sup.13 being optionally fused together to form a bridged structure.

Description

DETAILED DESCRIPTION OF CERTAIN EMBODIMENTS

(1) The present invention provides, among other things, metal complexes for the copolymerization of carbon dioxide and epoxides and methods of using the same. In certain embodiments, provided metal complexes contain a metal-salen complex tethered to two or more cationic activating moieties. In some embodiments, each activating moiety comprises a linker and one or more cationic functional groups. In some embodiments, provided metal complexes act as polymerization catalysts.

(2) In certain embodiments, the present invention encompasses metal complexes comprising a metal atom coordinated with a salen ligand, the salen ligand comprising two halves with each half coordinated to the metal atom via an imine and an oxygen atom wherein the metal complex is characterized in that one of the two halves of the salen ligand has two or more cationic activating moieties covalently tethered to it and the other half has no tethered activating moieties.

(3) In certain embodiments, the cationic activating moieties tethered to the ligand are independently selected from the group consisting of: onium salts, nitrogen-containing functional groups, phosphorous-containing functional groups, and arsenic-containing functional groups. In certain embodiments, at least one activating moiety comprises an ammonium salt. In certain embodiments, at least one activating moiety comprises a guanidinium salt. In certain embodiments, at least one activating moiety comprises an amidinium salt.

(4) In certain embodiments, the half of the ligand having no tethered cationic activating moieties is derived from salicylaldehyde optionally substituted with one or more aliphatic groups.

(5) In certain embodiments, the half of the ligand having no tethered cationic activating moieties comprises or is derived from a gamma dicarbonyl compound. In certain embodiments, a gamma dicarbonyl compound comprises optionally substituted acetylacetone. In certain embodiments, a gamma dicarbonyl compound comprises optionally substituted malonic acid derivative.

(6) In certain embodiments, the present invention encompasses metal complexes having a structure:

(7) ##STR00005##
wherein: M is a metal atom; X is a nucleophile capable of ring opening an epoxide; k is an integer from 0-2 inclusive; R represents one or more substituents optionally present on the phenyl rings and each R is independently selected from the group consisting of: halogen, NO.sub.2, CN, SR.sup.y, S(O)R.sup.y, S(O).sub.2R.sup.y, NR.sup.yC(O)R.sup.y, OC(O)R.sup.y, CO.sub.2R.sup.y, NCO, CNO, SiR.sub.3, N.sub.3, OR.sup.y, OC(O)N(R.sup.y).sub.2, N(R.sup.y).sub.2, NR.sup.yC(O)R.sup.y, NR.sup.yC(O)OR.sup.y, C(O)R.sup.y, C(O)N(R.sup.y).sub.2, SO.sub.2N(R.sup.y).sub.2, N(R.sup.y)C(O)N(R.sup.y).sub.2, N(R)SO.sub.2R; or an optionally substituted radical selected from the group consisting of C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur, where two or more adjacent R 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; R.sup.y at each occurrence is independently hydrogen, an optionally substituted radical selected the group consisting of acyl; C.sub.1-6 aliphatic; C.sub.1-6 heteroaliphatic; carbamoyl; arylalkyl; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; an oxygen protecting group; and a nitrogen protecting group, where two R groups on the same nitrogen atom can optionally be taken together to form an optionally substituted 3- to 7-membered ring; represents is an optionally substituted moiety linking the two nitrogen atoms of the diamine portion of the salen ligand, where is selected from the group consisting of phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an optionally substituted C.sub.2-20 aliphatic group, wherein one or more methylene units are optionally and independently replaced by NR.sup.y, N(R.sup.y)C(O), C(O)N(R.sup.y), OC(O)N(R.sup.y), N(R.sup.y)C(O)O, OC(O)O, O, C(O), OC(O), C(O)O, S, SO, SO.sub.2, C(S), C(NR.sup.y), C(NOR.sup.y) or NN; and (Z).sub.m represents one or more activating moieties, where is a covalent linker containing one or more atoms selected from the group consisting of C, O, N, S, and Si; Z is a cationic functional group and each m is independently an integer from 1 to 4 indicating the number of individual activating functional groups present in each activating moiety; wherein a total of at least two cationic functional groups (Z) are present on the metal complex.

(8) (i) Z Groups.

(9) As described above, Z groups are cationic functional groups, and metal complexes encompassed by the present invention have two or more such groups. Z groups typically contain at least one nitrogen, phosphorous, arsenic, or sulfur atom with a positive charge, though in some cases a Z group may have two or more such atoms or the positive charge may be delocalized across two or more atoms in the functional group through resonance structures. Each Z group may be the same or different.

(10) In certain embodiments, each cationic functional group (Z) is independently selected from the group consisting of:

(11) ##STR00006## ##STR00007## ##STR00008##
or a combination of two or more of these,
wherein: each occurrence of R.sup.1, R.sup.2, and R.sup.3 is independently hydrogen or an optionally substituted radical selected from the group consisting of C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; wherein any two or more R.sup.1, R.sup.2, and R.sup.3 groups can be taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more additional heteroatoms; R.sup.5 is R.sup.2 or hydroxyl; wherein R.sup.1 and R.sup.5 can be taken together with intervening atoms to form one or more optionally substituted carbocyclic, heterocyclic, aryl, or heteroaryl rings; each R.sup.6 and R.sup.7 is independently hydrogen or an optionally substituted radical selected from the group consisting of C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle; a 7- to 14-membered saturated or partially unsaturated polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; an 8- to 14-membered polycyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated monocyclic heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 14-membered saturated or partially unsaturated polycyclic heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; phenyl; or an 8- to 14-membered polycyclic aryl ring; wherein R.sup.6 and R.sup.7 can be taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more heteroatoms, and an R.sup.6 and R.sup.7 group can be taken with an R.sup.1 or R.sup.2 group to form one or more optionally substituted rings; each occurrence of R.sup.8 is independently selected from the group consisting of: halogen, NO.sub.2, CN, SR.sup.y, S(O)R.sup.y, S(O).sub.2R.sup.y, NR.sup.yC(O)R.sup.y, OC(O)R.sup.y, CO.sub.2R.sup.y, NCO, CNO, SiR.sub.3, N.sub.3, OR.sup.y, OC(O)N(R.sup.y).sub.2, N(R.sup.y).sub.2, NR.sup.yC(O)R.sup.y, NR.sup.yC(O)OR.sup.y, C(O)R.sup.y, C(O)N(R.sup.y).sub.2, SO.sub.2N(R.sup.y).sub.2, N(R.sup.y)C(O)N(R.sup.y).sub.2, N(R)SO.sub.2R; or an optionally substituted radical selected from the group consisting of C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle; a 7- to 14-membered saturated or partially unsaturated polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; an 8- to 14-membered polycyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated monocyclic heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 14-membered saturated or partially unsaturated polycyclic heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; phenyl; or an 8- to 14-membered polycyclic aryl ring; wherein each R.sup.y is independently as defined above and described in classes and subclasses herein, and where two or more adjacent R.sup.8 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; X.sup. is any anion; Ring A is an optionally substituted, 5- to 10-membered heteroaryl group; and Ring B is an optionally substituted, 3- to 8-membered saturated or partially unsaturated monocyclic heterocyclic ring having 0-2 heteroatoms in addition to the depicted ring nitrogen atom independently selected from nitrogen, oxygen, or sulfur.

(12) In certain embodiments, each cationic functional group (Z), is independently selected from the group consisting of:

(13) ##STR00009##
where X.sup. is any anion; R.sup.11, R.sup.12, R.sup.13, R.sup.21, R.sup.22, R.sup.23, R.sup.24 and R.sup.25 are each independently hydrogen; C.sub.1-C.sub.20 alkyl; C.sub.1-C.sub.20 alkyl having one or more functional moieties selected from the group consisting of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; C.sub.2-C.sub.20 alkenyl; C.sub.2-C.sub.20 alkenyl having one or more functional moieties selected from the group consisting of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; C.sub.7-C.sub.20 alkylaryl; C.sub.7-C.sub.20 alkylaryl having one or more functional moieties selected from the group consisting of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; C.sub.7-C.sub.20 arylalkyl; C.sub.7-C.sub.20 arylalkyl having one or more functional moieties selected from the group consisting of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; or a metalloid radical of group XIV metal substituted by hydrocarbyl, two of R.sup.11, R.sup.12 and R.sup.13, or two of R.sup.21, R.sup.22, R.sup.23, R.sup.24 and R.sup.25 being optionally fused together to form a bridged structure; R.sup.31, R.sup.32 and R.sup.33 are each independently hydrogen; C.sub.1-C.sub.20 alkyl; C.sub.1-C.sub.20 alkyl having one or more functional moieties selected from the group consisting of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; C.sub.2-C.sub.20 alkenyl; C.sub.2-C.sub.20 alkenyl having one or more functional moieties selected from the group consisting of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; C.sub.7-C.sub.20 alkylaryl; C.sub.7-C.sub.20 alkylaryl having one or more functional moieties selected from the group consisting of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; C.sub.7-C.sub.20 arylalkyl; C.sub.7-C.sub.20 arylalkyl having one or more functional moieties selected from the group consisting of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; or a metalloid radical of group XIV metal substituted by hydrocarbyl, two of R.sup.31, R.sup.32 and R.sup.33 being optionally fused together to form abridged structure; R is hydrogen; C.sub.1-C.sub.20 alkyl; C.sub.1-C.sub.20 alkyl having one or more functional moieties selected from the group consisting of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; C.sub.2-C.sub.20 alkenyl; C.sub.2-C.sub.20 alkenyl having one or more functional moieties selected from the group consisting of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; C.sub.7-C.sub.20 alkylaryl; C.sub.7-C.sub.20 alkylaryl having one or more functional moieties selected from the group consisting of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus; C.sub.7-C.sub.20 arylalkyl; C.sub.7-C.sub.20 arylalkyl having one or more functional moieties selected from the group consisting of halogen, nitrogen, oxygen, silicon, sulfur and phosphorus.

(14) It will be appreciated that for provided metal complexes and portions thereof, where a cationic group is depicted, a X.sup. counterion group is intended whether explicitly shown or not.

(15) In certain embodiments, at least one Z group is an ammonium group. In certain embodiments, a Z group comprises an alkylammonium group. In certain embodiments, a Z group has a formula:

(16) ##STR00010##
where R.sup.1, R.sup.2, R.sup.3 and X.sup. are as defined above. In certain embodiments, each R.sup.1, R.sup.2, and R.sup.3 group on the ammonium moiety is an alkyl group. In certain embodiments, each R.sup.1, R.sup.2, and R.sup.3 group is independently a C.sub.1-C.sub.20 straight chain, branched, or cyclic alkyl group. In certain embodiments, each R.sup.1, R.sup.2, and R.sup.3 group is independently a C.sub.1-C.sub.12 straight or branched alkyl group. In certain embodiments, each R.sup.1, R.sup.2, and R.sup.3 group is independently a C.sub.1-C.sub.8 straight or branched alkyl group. In certain embodiments, each R.sup.1, R.sup.2, and R.sup.3 group is independently a C.sub.1-C.sub.6 straight or branched alkyl group. In certain embodiments, each R.sup.1, R.sup.2, and R.sup.3 group is independently a C.sub.1-C.sub.6 n-alkyl group. In certain embodiments, each R.sup.1, R.sup.2, and R.sup.3 group is independently selected from the group consisting of: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, and n-hexyl. In certain embodiments, two or more of R.sup.1, R.sup.2, and R.sup.3 are taken together with the nitrogen atom to form a ring. Such compounds include analogs of known nitrogen heterocycles such as pyrrolidine, piperidine, morpholine, piperazine, dabco, quinuclidine and the like.

(17) In certain embodiments, a Z group comprises a heterocyclic ammonium group. In certain embodiments, such compounds comprise cationic heterocycles such as imidizolium, oxazolium, thiazolium, pyridinium, pyrimidinium and the like.

(18) In certain embodiments, at least one cationic activating functional group is a guanidinium group. In certain embodiments, such guanidinium groups have a structure:

(19) ##STR00011##
wherein each R.sup.1 and R.sup.2 is independently as defined above and described in classes and subclasses herein. In some embodiments, each R.sup.1 and R.sup.2 is independently hydrogen or optionally substituted C.sub.1-20 aliphatic. In some embodiments, each R.sup.1 and R.sup.2 is independently hydrogen or optionally substituted C.sub.1-10 aliphatic. In some embodiments, each R.sup.1 and R.sup.2 is independently hydrogen or C.sub.1-12 aliphatic. In some embodiments, each R.sup.1 and R.sup.2 is independently hydrogen or C.sub.1-20 heteroaliphatic. In some embodiments, each R.sup.1 and R.sup.2 is independently hydrogen or phenyl. In some embodiments, each R.sup.1 and R.sup.2 is independently hydrogen or 8- to 10-membered aryl. In some embodiments, each R.sup.1 and R.sup.2 is independently hydrogen or 5- to 10-membered heteroaryl. In some embodiments, each R.sup.1 and R.sup.2 is independently hydrogen or 3- to 7-membered heterocyclic. In some embodiments, one or more of R.sup.1 and R.sup.2 is optionally substituted C.sub.1-12 aliphatic.

(20) In some embodiments, where a Z group is a guanidium, any two or more R.sup.1 or R.sup.2 groups are taken together with intervening atoms to form one or more optionally substituted carbocyclic, heterocyclic, aryl, or heteroaryl rings. In certain embodiments, R.sup.1 and R.sup.2 groups are taken together to form an optionally substituted 5- or 6-membered ring. In some embodiments, three or more R.sup.1 and/or R.sup.2 groups are taken together to form an optionally substituted fused ring system.

(21) In certain embodiments, two R.sup.1 or R.sup.2 groups are taken together with intervening atoms to form a compound selected from:

(22) ##STR00012##
wherein each R.sup.1 and R.sup.2 is independently as defined above and described in classes and subclasses herein, and Ring G is an optionally substituted 5- to 7-membered saturated or partially unsaturated heterocyclic ring.

(23) In certain embodiments, multiple R.sup.1 and R.sup.2 groups are taken together with intervening atoms to form a bicyclic guanidinium group:

(24) ##STR00013##
wherein R.sup.1 is as defined above and described in classes and subclasses herein, and Ring G1 and G2 are independently optionally substituted 5- to 7-membered saturated or partially unsaturated heterocyclic rings.

(25) It will be appreciated that when a guanidinium cation is depicted as

(26) ##STR00014##
all such resonance forms are contemplated and encompassed by the present disclosure. For example, such groups can also be depicted as

(27) ##STR00015##

(28) In specific embodiments, a guanidinium activating functional group is selected from the group consisting of:

(29) ##STR00016## ##STR00017##

(30) In some embodiments, an activating functional group is a sulfonium group or an arsonium group:

(31) ##STR00018##
wherein each of R.sup.1, R.sup.2, and R.sup.3 are as defined above and described in classes and subclasses herein.

(32) In specific embodiments, an arsonium activating functional group is selected from the group consisting of:

(33) ##STR00019##

(34) In some embodiments, an activating functional group is an optionally substituted nitrogen-containing heterocycle. In certain embodiments, the nitrogen-containing heterocycle is an aromatic heterocycle. In certain embodiments, the optionally substituted nitrogen-containing heterocycle is selected from the group consisting of: pyridine, imidazole, pyrrolidine, pyrazole, quinoline, thiazole, dithiazole, oxazole, triazole, pyrazolem, isoxazole, isothiazole, tetrazole, pyrazine, thiazine, and triazine.

(35) In some embodiments, a nitrogen-containing heterocycle includes a quaternarized nitrogen atom. In certain embodiments, a nitrogen-containing heterocycle includes an iminium moiety such as

(36) ##STR00020##
In certain embodiments, the optionally substituted nitrogen-containing heterocycle is selected from the group consisting of pyridinium, imidazolium, pyrrolidinium, pyrazolium, quinolinium, thiazolium, dithiazolium, oxazolium, triazolium, isoxazolium, isothiazolium, tetrazolium, pyrazinium, thiazinium, and triazinium.

(37) In certain embodiments, a nitrogen-containing heterocycle is linked to a metal complex via a ring nitrogen atom. In some embodiments, a ring nitrogen to which the attachment is made is thereby quaternized, and in some embodiments, linkage to a metal complex takes the place of an NH bond and the nitrogen atom thereby remains neutral. In certain embodiments, an optionally substituted N-linked nitrogen-containing heterocycle is a pyridinium derivative. In certain embodiments, optionally substituted N-linked nitrogen-containing heterocycle is an imidazolium derivative. In certain embodiments, optionally substituted N-linked nitrogen-containing heterocycle is a thiazolium derivative. In certain embodiments, optionally substituted N-linked nitrogen-containing heterocycle is a pyridinium derivative.

(38) In some embodiments, an activating functional group is

(39) ##STR00021##
In certain embodiments, ring A is an optionally substituted, 5- to 10-membered heteroaryl group. In some embodiments, Ring A is an optionally substituted, 6-membered heteroaryl group. In some embodiments, Ring A is a ring of a fused heterocycle. In some embodiments, Ring A is an optionally substituted pyridyl group.

(40) In some embodiments, when Z is

(41) ##STR00022##
ring A is other than an imidazole, an oxazole, or a thiazole.

(42) In specific embodiments, a nitrogen-containing heterocycle activating functional group is selected from the group consisting of:

(43) ##STR00023## ##STR00024##

(44) In certain embodiments, Ring B is a 5-membered saturated or partially unsaturated monocyclic heterocyclic ring. In certain embodiments, Ring B is a 6-membered saturated or partially unsaturated heterocycle. In certain embodiments, Ring B is a 7-membered saturated or partially unsaturated heterocycle. In certain embodiments, Ring B is tetrahydrofuranyl, tetrahydrothienyl, pyrrolidinyl, pyrrolidonyl, piperidinyl, pyrrolinyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, decahydroquinolinyl, oxazolidinyl, piperazinyl, dioxanyl, dioxolanyl, diazepinyl, oxazepinyl, thiazepinyl, morpholinyl, and quinuclidinyl. In some embodiments, Ring B is piperidinyl.

(45) In some embodiments, an activating functional group an amidinum group. In certain embodiments an amidinium Z group is

(46) ##STR00025##
where each R.sup.1, R.sup.2, and R.sup.3 is independently as defined above and described in classes and subclasses herein.

(47) In some embodiments, an amidinium Z group is

(48) ##STR00026##
wherein each R.sup.1 and R.sup.2 is independently as defined above and described in classes and subclasses herein.

(49) In certain embodiments where a Z group is an amidinium, R.sup.1 and R.sup.2 groups are taken together with intervening atoms to form a compound selected from:

(50) ##STR00027##
wherein each R.sup.1 and R.sup.2 is independently as defined above and described in classes and subclasses herein, and Ring G is an optionally substituted, 5- to 7-membered saturated or partially unsaturated heterocyclic ring.

(51) In certain embodiments, multiple R.sup.1 and R.sup.2 groups are taken together with intervening atoms to form a bicyclic amidinium group:

(52) ##STR00028##
wherein R.sup.1 is as defined above and described in classes and subclasses herein, and Ring G1 and G2 are independently optionally substituted 5- to 7-membered saturated or partially unsaturated heterocyclic rings.

(53) In certain embodiments, an activating functional group is selected from the group consisting of:

(54) ##STR00029##

(55) In some embodiments, an activating functional group is

(56) ##STR00030##
wherein each R.sup.1, R.sup.2, and R.sup.3 is independently as defined above and described in classes and subclasses herein.

(57) In some embodiments, an activating functional group is

(58) ##STR00031##
wherein each of R.sup.1, R.sup.2, R.sup.6, and R.sup.7 is as defined above and described in classes and subclasses herein. In certain embodiments, R.sup.6 and R.sup.7 are each independently an optionally substituted group selected from the group consisting of C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic; phenyl, and 8-10-membered aryl. In some embodiments, R.sup.6 and R.sup.7 are each independently an optionally substituted C.sub.1-20 aliphatic. In some embodiments, R.sup.6 and R.sup.7 are each independently an optionally substituted C.sub.1-20 heteroaliphatic having. In some embodiments, R.sup.6 and R.sup.7 are each independently an optionally substituted phenyl or 8-10-membered aryl. In some embodiments, R.sup.6 and R.sup.7 are each independently an optionally substituted 5- to 10-membered heteroaryl. In some embodiments, R.sup.6 and R.sup.7 can be taken together with intervening atoms to form one or more rings selected from the group consisting of: optionally substituted C.sub.3-C.sub.14 carbocycle, optionally substituted C.sub.3-C.sub.14 heterocycle, optionally substituted C.sub.6-C.sub.10 aryl, and optionally substituted 5- to 10-membered heteroaryl. In some embodiments, R.sup.6 and R.sup.7 are each independently an optionally substituted C.sub.1-6 aliphatic. In some embodiments, each occurrence of R.sup.6 and R.sup.7 is independently methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, or benzyl. In some embodiments, each occurrence of R.sup.6 and R.sup.7 is independently perfluoro. In some embodiments, each occurrence of R.sup.6 and R.sup.7 is independently CF.sub.2CF.sub.3.

(59) In some embodiments, an activating functional group is

(60) ##STR00032##
wherein each R.sup.1 and R.sup.2 is independently as defined above and described in classes and subclasses herein, both singly and in combination.

(61) In some embodiments, an activating functional group is

(62) ##STR00033##
wherein each R.sup.1, R.sup.2, and R is independently as defined above and described in classes and subclasses herein.

(63) In some embodiments, an activating functional group is

(64) ##STR00034##
wherein each R.sup.1 and R.sup.2 is independently as defined above and described in classes and subclasses herein.

(65) In some embodiments, an activating functional group is

(66) ##STR00035##
wherein each R.sup.1 and R.sup.2 is independently as defined above and described in classes and subclasses herein.

(67) In some embodiments, an activating functional group is

(68) ##STR00036##
wherein each R.sup.1, R.sup.2, and R.sup.3 is independently as defined above and described in classes and subclasses herein.

(69) In some embodiments, an activating functional group is

(70) ##STR00037##
wherein each R.sup.1 and R.sup.2 is independently as defined above and described in classes and subclasses herein.

(71) (ii) Linkers and Aryl Ring Substitution Patterns

(72) As noted above, metal complexes of the present invention comprise two or more of the Z groups just described. These Z groups are attached to only one of the two aryl rings comprising the salen ligand. This situation can result from having two or more (Z).sub.m groups attached to one aryl ring, or can result from having one (Z).sub.m group where is m is 2 or more.

(73) In certain embodiments, metal complexes of the present invention comprise two (Z).sub.m groups attached to one aryl ring of a salen ligand. In certain embodiments, such metal complexes have a formula II:

(74) ##STR00038##

(75) where R, M, X, , Z, k, and m are as defined above, and each (Z).sub.m group may be the same or different.

(76) In certain embodiments where a metal complex conforms to formula II, no R groups are present on the phenyl ring bearing the (Z).sub.m groups.

(77) In certain embodiments, metal complexes of the present invention comprise one (Z).sub.m group where m is greater than 1. In certain embodiments of such metal complexes, m is 2. In certain embodiments of such metal complexes, m is 3. In certain embodiments, such metal complexes have a formula IIIa or IIIb:

(78) ##STR00039##
where R, M, X, , Z, and k are as defined above, and m is greater than 1.

(79) As described above, each activating moiety (Z).sub.m comprises a linker coupled to at least one activating functional group Z, with m denoting the number of activating functional groups present on a single linker moiety.

(80) As noted above there may be one or more activating moiety (Z).sub.m tethered to a given metal complex. Similarly, each activating moiety itself may contain more than one activating functional group Z. In certain embodiments, each activating moiety contains only one activating functional group (i.e. m=1). In some embodiments, each activating moiety contains more than one activating functional groups (i.e. m>1). In certain embodiments, an activating moiety contains two activating functional groups (i.e. m=2). In certain embodiments, an activating moiety contains three activating functional groups (i.e. m=3). In certain embodiments, an activating moiety contains four activating functional groups (i.e. m=4). In certain embodiments where more than one activating functional group is present on an activating moiety, they are all the same functional group. In some embodiments where more than one activating functional group is present on an activating moiety, two or more of the activating functional groups are different.

(81) In certain embodiments, each linker moiety contains 1-30 atoms including at least one carbon atom, and optionally one or more atoms selected from the group consisting of N, O, S, Si, B, and P.

(82) In certain embodiments, the linker is an optionally substituted C.sub.2-30 aliphatic group wherein one or more methylene units are optionally and independently replaced by NR.sup.y, N(R.sup.y)C(O), C(O)N(R.sup.y), O, C(O), OC(O), C(O)O, S, SO, SO.sub.2, C(S), C(NR.sup.y), or NN, where each occurrence of R.sup.y is independently H, or an optionally substituted radical selected from the group consisting of C.sub.1-6 aliphatic, 3- to 7-membered heterocyclic, phenyl, and 8- to 10-membered aryl. In certain embodiments, a linker moiety is a C.sub.4-C.sub.12 aliphatic group substituted with one or more moieties selected from the group consisting of halogen, NO.sub.2, CN, SR.sup.y, S(O)R.sup.y, S(O).sub.2R.sup.y, NR.sup.yC(O)R.sup.y, OC(O)R.sup.y, CO.sub.2R.sup.y, NCO, CNO, SiR.sub.3, N.sub.3, OR.sup.y, OC(O)N(R.sup.y).sub.2, N(R.sup.y).sub.2, NR.sup.yC(O)R.sup.y, NR.sup.yC(O)OR.sup.y, C(O)R.sup.y, C(O)N(R.sup.y).sub.2, SO.sub.2N(R.sup.y).sub.2, N(R.sup.y)C(O)N(R.sup.y).sub.2, N(R)SO.sub.2R; where R.sup.y is H, or an optionally substituted radical selected from the group consisting of C.sub.1-6 aliphatic 3- to 7-membered heterocyclic, phenyl, and 8- to 10-membered aryl.

(83) In certain embodiments, a linker moiety is an optionally substituted C.sub.3-C.sub.30 aliphatic group. In certain embodiments, a linker is an optionally substituted C.sub.4-24 aliphatic group. In certain embodiments, a linker moiety is an optionally substituted C.sub.4-C.sub.20 aliphatic group. In certain embodiments, a linker moiety is an optionally substituted C.sub.4-C.sub.12 aliphatic group. In certain embodiments, a linker is an optionally substituted C.sub.4-10 aliphatic group. In certain embodiments, a linker is an optionally substituted C.sub.4-8 aliphatic group. In certain embodiments, a linker moiety is an optionally substituted C.sub.4-C.sub.6 aliphatic group. In certain embodiments, a linker moiety is an optionally substituted C.sub.6-C.sub.12 aliphatic group. In certain embodiments, a linker moiety is an optionally substituted C.sub.8 aliphatic group. In certain embodiments, a linker moiety is an optionally substituted C.sub.7 aliphatic group. In certain embodiments, a linker moiety is an optionally substituted C.sub.6 aliphatic group. In certain embodiments, a linker moiety is an optionally substituted C.sub.5 aliphatic group. In certain embodiments, a linker moiety is an optionally substituted C.sub.4 aliphatic group. In certain embodiments, a linker moiety is an optionally substituted C.sub.3 aliphatic group. In certain embodiments, a aliphatic group in the linker moiety is an optionally substituted straight alkyl chain. In certain embodiments, the aliphatic group is an optionally substituted branched alkyl chain. In some embodiments, a linker moiety is a C.sub.4 to C.sub.20 alkyl group having one or more methylene groups replaced by C(R.sup.aR.sup.b) where R.sup.a and R.sup.b are each independently C.sub.1-C.sub.4 alkyl groups. In certain embodiments, a linker moiety consists of an aliphatic group having 4 to 30 carbons including one or more gcm-dimethyl substituted carbon atoms.

(84) In certain embodiments, a linker moiety includes one or more optionally substituted cyclic elements selected from the group consisting of saturated or partially unsaturated carbocyclic, aryl, heterocyclic, or heteroaryl. In certain embodiments, a linker moiety consists of the substituted cyclic element, in some embodiments the cyclic element is part of a linker with one or more non-ring heteroatoms or optionally substituted aliphatic groups comprising other parts of the linker moiety.

(85) In some embodiments, a linker moiety is of sufficient length to allow one or more activating functional groups to be positioned near a metal atom of a metal complex. In certain embodiments, structural constraints are built into a linker moiety to control the disposition and orientation of one or more activating functional groups near a metal center of a metal complex. In certain embodiments such structural constraints are selected from the group consisting of cyclic moieties, bicyclic moieties, bridged cyclic moieties and tricyclic moieties. In some embodiments, such structural constraints are the result of acyclic steric interactions. In certain embodiments such structural constraints are selected from the group consisting of cis double bonds, trans double bonds, cis allenes, trans allenes, and triple bonds. In some embodiments, such structural constraints are selected from the group consisting of substituted carbons including geminally disubstituted groups such as spirocyclic rings, gem dimethyl groups, gem diethyl groups and gem diphenyl groups. In certain embodiments such structural constraints are selected from the group consisting of heteroatom-containing functional groups such as sulfoxides, amides, and oximes.

(86) In certain embodiments, linker moieties are selected from the group consisting of:

(87) ##STR00040## ##STR00041##

(88) where * represents the site of attachment to a ligand, and each # represents a site of attachment of an activating functional group.

(89) In some embodiments, s is 0. In some embodiments, s is 1. In some embodiments, s is 2. In some embodiments, s is 3. In some embodiments, s is 4. In some embodiments, s is 5. In some embodiments, s is 6.

(90) In some embodiments, t is 1. In some embodiments, t is 2. In some embodiments, t is 3. In some embodiments, t is 4.

(91) In some embodiments of provided metal complexes, each R.sup.y is H, or an optionally substituted radical selected from the group consisting of C.sub.1-6 aliphatic, 3- to 7-membered heterocyclic, phenyl, and 8- to 10-membered aryl. In some embodiments, an R.sup.y group attached to a nitrogen, oxygen, or sulfur atom on a provided metal complex is other than hydrogen.

(92) In some embodiments of provided metal complexes, each R is H, or an optionally substituted radical selected from the group consisting of C.sub.1-6 aliphatic, 3- to 7-membered heterocyclic, phenyl, and 8- to 10-membered aryl. In some embodiments, an R group attached to a nitrogen, oxygen, or sulfur atom on a provided metal complex is other than hydrogen.

(93) In some embodiments, an activating moiety (Z).sub.m has a formula,

(94) ##STR00042##
where R.sup.1, *, s, and Z are as defined above. In certain embodiments, an activating moiety has a formula

(95) ##STR00043##
where *, s, and Z are as defined above. In certain embodiments, an activating moiety has a formula

(96) ##STR00044##
where *, s, and Z are as defined above and described in classes and subclasses herein.

(97) In certain embodiments, an activating moiety has a formula selected from the group consisting of:

(98) ##STR00045##
where Z and * are as defined above and described in classes and subclasses herein.

(99) In certain embodiments, an activating moiety has a formula selected from the group consisting of:

(100) ##STR00046##
where Z, and * are as defined above and described in classes and subclasses herein.

(101) In certain embodiments, an activating moiety has a formula selected from the group consisting of:

(102) ##STR00047##
where *, #, and s are as defined above and described in classes and subclasses herein. In certain embodiments, an activating moiety has a formula selected from the group consisting of:

(103) ##STR00048##
where Z, and * are as defined above and described in classes and subclasses herein.

(104) In certain embodiments, an activating moiety has a formula selected from the group consisting of:

(105) ##STR00049##
where Z and * are as defined above and described in classes and subclasses herein.

(106) (iii) Metal Complexes

(107) Metal complexes of the present invention conform the general formula I:

(108) ##STR00050##
wherein: M is a metal atom; X is a nucleophile capable of ring opening an epoxide; k is an integer from 0-2 inclusive; R represents one or more substituents optionally present on the phenyl rings and each R is independently selected from the group consisting of: halogen, NO.sub.2, CN, SR.sup.y, S(O)R.sup.y, S(O).sub.2R.sup.y, NR.sup.yC(O)R.sup.y, OC(O)R.sup.y, CO.sub.2R.sup.y, NCO, CNO, SiR.sub.3, N.sub.3, OR.sup.y, OC(O)N(R.sup.y).sub.2, N(R.sup.y).sub.2, NR.sup.yC(O)R.sup.y, NR.sup.yC(O)OR.sup.y, C(O)R.sup.y, C(O)N(R.sup.y).sub.2, SO.sub.2N(R.sup.y).sub.2, N(R.sup.y)C(O)N(R.sup.y).sub.2, N(R)SO.sub.2R; or an optionally substituted radical selected from the group consisting of C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur, where two or more adjacent R 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; R.sup.y at each occurrence is independently hydrogen, an optionally substituted radical selected the group consisting of acyl; C.sub.1-6 aliphatic; C.sub.1-6 heteroaliphatic; carbamoyl; arylalkyl; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; an oxygen protecting group; and a nitrogen protecting group, where two R groups on the same nitrogen atom can optionally be taken together to form an optionally substituted 3- to 7-membered ring; represents is an optionally substituted moiety linking the two nitrogen atoms of the diamine portion of the salen ligand, where is selected from the group consisting of phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an optionally substituted C.sub.2-20 aliphatic group, wherein one or more methylene units are optionally and independently replaced by NR.sup.y, N(R.sup.y)C(O), C(O)N(R.sup.y), OC(O)N(R.sup.y), N(R.sup.y)C(O)O, OC(O)O, O, C(O), OC(O), C(O)O, S, SO, SO.sub.2, C(S), C(NR.sup.y), C(NOR.sup.y) or NN; (Z).sub.m represents one or more activating moieties, where is a covalent linker containing one or more atoms selected from the group consisting of C, O, N, S, and Si; Z is a activating functional group and each m is independently an integer from 1 to 4 indicating the number of individual activating functional groups present in each activating moiety.

(109) In certain embodiments of provided metal complexes, a metal complex has a structure selected from the group consisting of:

(110) ##STR00051## wherein: R.sup.1a and R.sup.1a, are independently hydrogen, or an optionally substituted radical selected from the group consisting of C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; R.sup.4a, R.sup.4a, R.sup.5a, R.sup.5a, R.sup.6a, R.sup.6a, R.sup.7a, and R.sup.7a are each independently a (Z).sub.m group, hydrogen, halogen, NO.sub.2, CN, SR.sup.y, S(O)R.sup.y, S(O).sub.2R.sup.y, NR.sup.yC(O)R.sup.y, OC(O)R.sup.y, CO.sub.2R.sup.y, NCO, CNO, SiR.sub.3, N.sub.3, OR.sup.y, OC(O)N(R.sup.y).sub.2, N(R.sup.y).sub.2, NR.sup.yC(O)R.sup.y, NR.sup.yC(O)OR.sup.y, C(O)R.sup.y, C(O)N(R.sup.y).sub.2, SO.sub.2N(R.sup.y).sub.2, N(R.sup.y)C(O)N(R.sup.y).sub.2, N(R)SO.sub.2R; or an optionally substituted radical selected from the group consisting of C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; wherein [R.sup.1a and R.sup.4a], [R.sup.1a and R.sup.4a] and any two adjacent R.sup.4a, R.sup.4a, R.sup.5a, R.sup.5a, R.sup.6a, R.sup.6a, R.sup.7a, and R.sup.7a groups can be taken together with intervening atoms to form one or more optionally substituted rings; R.sup.d at each occurrence is independently halogen, OR, NR.sub.2, SR, CN, NO.sub.2, SO.sub.2R, SOR, SO.sub.2NR.sub.2; CNO, NRSO.sub.2R, NCO, N.sub.3, SiR.sub.3; or an optionally substituted radical selected from the group consisting of C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; where two or more R.sup.d groups may be taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more heteroatoms, R.sup.c at each occurrence is independently halogen, OR, NR.sub.2, SR, CN, NO.sub.2, SO.sub.2R, SOR, SO.sub.2NR.sub.2; CNO, NRSO.sub.2R, NCO, N.sub.3, SiR.sub.3; or an optionally substituted radical selected from the group consisting of C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; where two or more R.sup.c groups may be taken together with the carbon atoms to which they are attached and any intervening atoms to form one or more optionally substituted rings; when two R.sup.c groups are attached to the same carbon atom, they may optionally be taken together along with the carbon atom to which they are attached to form an optionally substituted moiety selected from the group consisting of: a 3- to 8-membered spirocyclic ring, a carbonyl, an oxime, a hydrazone, and an imine; n is 0 or an integer from 1 to 4, inclusive; p is 0 or an integer from 1 to 6, inclusive; R at each occurrence is independently hydrogen, an optionally substituted radical selected the group consisting of acyl; C.sub.1-6 aliphatic; C.sub.1-6 heteroaliphatic; carbamoyl; arylalkyl; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; an oxygen protecting group; and a nitrogen protecting group, where two R groups on the same nitrogen atom can optionally be taken together to form an optionally substituted 3- to 7-membered ring, wherein the metal complex comprises at least two Z groups, and wherein only one of the two aromatic rings denoted A and B in the structures above has a substituent that is a (Z).sub.m.

(111) In some embodiments, M is Co.

(112) In some embodiments, R.sup.1a, R.sup.1a, R.sup.4a, R.sup.4a, R.sup.6a, and R.sup.6a are each H. In some embodiments, R.sup.5a, R.sup.5a, R.sup.7a and R.sup.7a are each optionally substituted C.sub.1-C.sub.12 aliphatic. In some embodiments, R.sup.4a, R.sup.4a, R.sup.5a, R.sup.5a, R.sup.6a, R.sup.6a, R.sup.7a, and R.sup.7a are each independently selected from the group consisting of: H, SiR.sub.3; methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, t-butyl, isoamyl, t-amyl, thexyl, and trityl. In some embodiments, R.sup.1a, R.sup.1a, R.sup.4a, R.sup.4a, R.sup.6a, and R.sup.6a are each H. In some embodiments, R.sup.7a is selected from the group consisting of H; methyl; ethyl; n-propyl; i-propyl; n-butyl; sec-butyl; t-butyl; isoamyl; t-amyl; thexyl; and trityl. In some embodiments, R.sup.5a and R.sup.7a are independently selected from the group consisting of H; methyl; ethyl; n-propyl; i-propyl; n-butyl; sec-butyl; t-butyl; isoamyl; t-amyl; thexyl; and trityl. In certain embodiments, one or more of R.sup.5a, R.sup.5a, R.sup.7a and R.sup.7a is a (Z).sub.m group. In some embodiments, R.sup.5a and R.sup.5a are a (Z).sub.m group.

(113) In certain embodiments, a provided metal complex has a structure selected from the group consisting of:

(114) ##STR00052##

(115) wherein R.sup.1a, R.sup.1a, R.sup.4a, R.sup.4a, R.sup.5a, R.sup.5a, R.sup.6a, R.sup.6a, R.sup.7a, R.sup.7a, M, and X are as defined above and described in classes and subclasses herein, wherein the metal complex comprises at least two Z groups and wherein only one of the two aromatic rings denoted A and B in the structures above has a substituent that is a (Z).sub.m group.

(116) In certain embodiments of complexes having formulae described above, one of the phenyl rings denoted A or B in the structures above is selected from the group consisting of:

(117) ##STR00053## ##STR00054## ##STR00055## ##STR00056## wherein (Z).sub.m represents one or more independently-defined activating moieties which may be bonded to any one or more unsubstituted positions of the phenyl ring and wherein a total of at least two Z groups are present.

(118) In certain embodiments, there is an activating moiety tethered to the position ortho to a metal-bound oxygen substituent of one of the salicylaldehyde-derived phenyl rings of a salen ligand as in formula IIIa-1:

(119) ##STR00057##
wherein: M, X, k, R, R, , and (Z).sub.m are as defined above and described in classes and subclasses herein, and R.sup.4a, R.sup.5a, and R.sup.6a are each independently a (Z).sub.m group, hydrogen, halogen, OR, NR.sub.2, SR, CN, NO.sub.2, SO.sub.2R, SOR, SO.sub.2NR.sub.2; CNO, NRSO.sub.2R, NCO, N.sub.3, SiR.sub.3; or an optionally substituted radical selected from the group consisting of C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; wherein any two adjacent R.sup.4a, R.sup.5a, and R.sup.6a groups can be taken together with intervening atoms to form one or more optionally substituted rings; and wherein each m is independently an integer greater than 1.

(120) In certain embodiments of compounds having formula IIIa-1 R.sup.4a, and R.sup.6a are each hydrogen, and R.sup.5a, is optionally substituted C.sub.1-C.sub.20 aliphatic.

(121) In certain embodiments of complexes IIIa-1, one of the phenyl rings comprising a salicylaldehyde-derived portion of a metal complex is selected from the group consisting of:

(122) ##STR00058## ##STR00059##

(123) where (Z) is as defined above and described in classes and subclasses herein, and m is greater than 1.

(124) In certain embodiments, there is an activating moiety tethered to the position para to the phenolic oxygen of one of the salicylaldehyde-derived phenyl rings of the salen ligand as in structure IVa:

(125) ##STR00060## where M, X, k, R, R.sup.4a, R.sup.6a, R.sup.7a, , and (Z).sub.m are as defined above and described in classes and subclasses herein.

(126) In certain embodiments of compounds having formula IVa, R.sup.4a and R.sup.6a are hydrogen, and R.sup.7a is optionally substituted C.sub.1-C.sub.20 aliphatic.

(127) In certain embodiments of metal complexes IVa, a phenyl ring comprising a salicylaldehyde-derived portion of a metal complex is selected from the group consisting of:

(128) ##STR00061## ##STR00062##
where (Z) is as defined above and described in classes and subclasses herein, and m is greater than 1.

(129) In some embodiments, there is an activating moiety tethered to the position para to the imine substituent of one of the salicylaldehyde-derived phenyl rings of a salen ligand as in formulae Va:

(130) ##STR00063##
where M, X, k, R, R.sup.4a, R.sup.5a, R.sup.7a, , and (Z).sub.m are as defined above and described in classes and subclasses herein.

(131) In certain embodiments of compounds having formula Va, R.sup.4 is hydrogen, and each of R.sup.5a and R.sup.7a is, independently, hydrogen or optionally substituted C.sub.1-C.sub.20 aliphatic.

(132) In certain embodiments of metal complexes Va, one of the phenyl rings comprising a salicylaldehyde-derived portion of a metal complex is selected from the group consisting of:

(133) ##STR00064## ##STR00065## ##STR00066##
where (Z) is as defined above and described in classes and subclasses herein, and m is greater than 1.

(134) In some embodiments, there is an activating moiety tethered to the position ortho to the imine substituent of one or both of the salicylaldehyde-derived phenyl rings of a salen ligand as in formula VIa:

(135) ##STR00067##
or, where X, k, M, R, R.sup.5a, R.sup.6a, R.sup.7a, , and (Z).sub.m are as defined above and described in classes and subclasses herein.

(136) In certain embodiments of compounds having formulae VIa, R.sup.6a is hydrogen, and each of R.sup.5a and R.sup.7a is, independently, hydrogen or optionally substituted C.sub.1-C.sub.20 aliphatic.

(137) In certain embodiments of metal complexes VIa one of the phenyl rings is selected from the group consisting of:

(138) ##STR00068## ##STR00069##
where (Z) is as defined above and described in classes and subclasses herein, and m is greater than 1.

(139) In some embodiments, there are activating moieties tethered to the positions ortho and para to the phenolic oxygen of one salicylaldehyde-derived phenyl ring of a salen ligand as in formula VIIa:

(140) ##STR00070##
where M, X, k, R, R.sup.4a, R.sup.6a, , and (Z).sub.m are as defined above and described in classes and subclasses herein.

(141) In certain embodiments of compounds having formula VIIa each of R.sup.6a and R.sup.4a is, independently, hydrogen or optionally substituted C.sub.1-C.sub.20 aliphatic.

(142) In certain embodiments of compounds having formula VIIa, each R.sup.6a and R.sup.4a is hydrogen.

(143) In some embodiments, there are activating moieties tethered to the positions ortho and para to the imine substituent of one of the salicylaldehyde-derived phenyl rings of a salen ligand as in formula VIIIa:

(144) ##STR00071##
where X, k, M, R, R.sup.5a, R.sup.7a, , and (Z).sub.m are as defined above and described in classes and subclasses herein.

(145) In certain embodiments of compounds having formula VIIIa each of R.sup.5a and R.sup.7a is independently hydrogen or substituted C.sub.1-C.sub.20 aliphatic.

(146) In certain embodiments of the present invention, metal complexes of structure VIIIa one of the phenyl rings comprising the salicylaldehyde-derived portion of a metal complex is independently selected from the group consisting of:

(147) ##STR00072## ##STR00073## ##STR00074## ##STR00075## ##STR00076##
where (Z) is as defined above and described in classes and subclasses herein and each m is, independently, 1, 2, 3, or 4.

(148) As shown above, the two phenyl rings derived from salicylaldehyde in the core salen structures are not the same. The phenyl ring not bearing any (Z).sub.m groups may be substituted or unsubstituted. If substituted, one or more R groups may be present as described above and in the examples and embodiments herein. In certain embodiments, the phenyl ring not bearing any (Z).sub.m groups conforms to the structure:

(149) ##STR00077##
Where each R group is the same or different.

(150) In certain embodiments, the phenyl ring not bearing any (Z).sub.m groups is substituted with one or two optionally substituted C.sub.1-20 aliphatic groups. In certain embodiments, the phenyl ring not bearing any (Z).sub.m groups is substituted with one optionally substituted C.sub.1-20 aliphatic group. In certain embodiments, the optionally substituted C.sub.1-20 aliphatic group is at the position ortho to the phenol. In certain the optionally substituted C.sub.1-20 aliphatic group is at the position para to the phenol. In certain embodiments, the phenyl ring not bearing any (Z).sub.m groups is substituted with two optionally substituted C.sub.1-20 aliphatic groups. In certain embodiments, the two optionally substituted C.sub.1-20 aliphatic groups are the same. In certain embodiments, the two optionally substituted C.sub.1-20 aliphatic groups are different. In certain embodiments, the two optionally substituted C.sub.1-20 aliphatic groups are at the positions ortho and para to the phenol.

(151) In certain embodiments, the phenyl ring not bearing any (Z).sub.m groups is selected from the group consisting of:

(152) ##STR00078## ##STR00079## ##STR00080##

(153) In certain embodiments, metallosalenate complexes of the present invention include, but are not limited to those in Table 1 below:

(154) TABLE-US-00001 TABLE 1 0 00 01 02 03 04 05 06 07 08 09 0 0 0 0 0 0 0 0 0 00 01 02 03 04 05 06 07 08 09 0 0 0 0 0

(155) Metal Atoms

(156) In certain embodiments, M is a metal atom selected from periodic table groups 3-13, inclusive. In certain embodiments, M is a transition metal selected from periodic table groups 5-12, inclusive. In certain embodiments, M is a transition metal selected from periodic table groups 4-11, inclusive. In certain embodiments, M is a transition metal selected from periodic table groups 5-10, inclusive. In certain embodiments, M is a transition metal selected from periodic table groups 7-9, inclusive. In some embodiments, M is selected from the group consisting of Cr, Mn, V, Fe, Co, Mo, W, Ru, Al, and Ni. In some embodiments, M is a metal atom selected from the group consisting of: cobalt; chromium; aluminum; titanium; ruthenium, and manganese. In some embodiments, M is cobalt. In some embodiments, M is chromium. In some embodiments, M is aluminum.

(157) In certain embodiments, a metal complex is a zinc, cobalt, chromium, aluminum, titanium, ruthenium, or manganese complex. In certain embodiments, a metal complex is an aluminum complex. In some embodiments, a metal complex is a chromium complex. In some embodiments, a metal complex is a zinc complex. In certain some embodiments, a metal complex is a titanium complex. In some embodiments, a metal complex is a ruthenium complex. In certain embodiments, a metal complex is a manganese complex. In certain embodiments, a metal complex is cobalt complex. In certain embodiments where the metal complex is a cobalt complex, the cobalt metal has an oxidation state of 3+ (i.e., Co(III)). In some embodiments, the cobalt metal has an oxidation state of 2+.

(158) In certain embodiments, at least one activating moiety is tethered to a carbon atom of one phenyl ring of the salicylaldehyde-derived portions of a salen ligand. In certain embodiments, at least one activating moiety is tethered to one or more carbon atoms of only one phenyl ring of the salicylaldehyde-derived portions of a salen ligand, as shown in formula I:

(159) In certain embodiments, for complexes of Table 1, M is CoX, where X is as defined above and described in classes and subclasses herein. In certain embodiments, for complexes of Table 1, M is CoOC(O)CF.sub.3. In certain embodiments, for complexes of Table 1, M is CoOAc. In certain embodiments, for complexes of Table 1, M is CoOC(O)C.sub.6F.sub.5. In certain embodiments, for complexes of Table 1, M is CoN.sub.3. In certain embodiments, for complexes of Table 1, M is CoNO.sub.3. In certain embodiments, for complexes of Table 1, M is CoCl. In certain embodiments, for complexes of Table 1, M is Co-nitrophenoxy. In certain embodiments, for complexes of Table 1, M is Co-dinitrophenoxy.

(160) In some embodiments, for complexes of Table 1, M is CrX, where X is as defined above and described in classes and subclasses herein.

(161) Polymerization Methods

(162) In another aspect, the present invention provides methods of making aliphatic polycarbonates. In certain embodiments, the methods comprise contacting one or more epoxides with CO.sub.2 in the presence of any of the metal complexes described hereinabove.

(163) In some embodiments, the present invention provides a method of polymerization, the method comprising: a) providing an epoxide of formula:

(164) ##STR00252## wherein: R.sup.a is hydrogen or an optionally substituted radical selected from the group consisting of C.sub.1-30 aliphatic; C.sub.1-30 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and each of R.sup.b, R.sup.c, and R.sup.d is independently hydrogen or an optionally substituted radical selected from the group consisting of C.sub.1-12 aliphatic; C.sub.1-12 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; wherein any of (R.sup.a and R.sup.c), (R.sup.c and R.sup.d), and (R.sup.a and R.sup.b) can be taken together with intervening atoms to form one or more optionally substituted rings; b) contacting the epoxide and carbon dioxide in the presence of a metal complex as described herein to provide a polymer having a formula selected from the group consisting of:

(165) ##STR00253##

(166) In some embodiments, a provided polymer has a formula:

(167) ##STR00254##
In some embodiments, a provided polymer has a formula:

(168) ##STR00255##
In some embodiments, carbon dioxide is optional and a provided polymer has a formula:

(169) ##STR00256##

(170) In some embodiments, the epoxide is ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, or mixtures of any of these. In some embodiments, the epoxide is propylene oxide. In some embodiments, the epoxide is ethylene oxide. In some embodiments, the epoxide is a mixture of propylene oxide with one or more of ethylene oxide, cyclohexene oxide, and butylene oxide. In certain embodiments, the epoxide is a mixture of ethylene oxide and propylene oxide. In some embodiments, the epoxide is a mixture of propylene oxide and cyclohexene oxide.

(171) In certain embodiments, R.sup.b, R.sup.c, and R.sup.d are each hydrogen. In some embodiments, R.sup.a is optionally substituted C.sub.1-12 aliphatic. In some embodiments, R.sup.a is optionally substituted C.sub.1-12 heteroaliphatic.

(172) In certain embodiments, one of R.sup.a, R.sup.b, R.sup.c, and R.sup.d is hydrogen. In certain embodiments, two of R.sup.a, R.sup.b, R.sup.c, and R.sup.d are hydrogen. In certain embodiments, three of R.sup.a, R.sup.b, R.sup.c, and R.sup.d are hydrogen.

(173) In certain embodiments, R.sup.a is hydrogen. In certain embodiments, R.sup.b is hydrogen. In certain embodiments, R.sup.c is hydrogen. In certain embodiments, R.sup.d is hydrogen.

(174) In certain embodiments, R.sup.a, R.sup.b, R.sup.c, and R.sup.d are each independently an optionally substituted C.sub.1-30 aliphatic group. In certain embodiments, R.sup.a, R.sup.b, R.sup.c, and R.sup.d are each independently an optionally substituted C.sub.1-20 aliphatic group. In certain embodiments, R.sup.a, R.sup.b, R.sup.c, and R.sup.d are each independently an optionally substituted C.sub.1-12 aliphatic group. In certain embodiments, R.sup.a, R.sup.b, R.sup.c, and R.sup.d are each independently an optionally substituted C.sub.1-8 aliphatic group. In certain embodiments, R.sup.a, R.sup.b, R.sup.c, and R.sup.d are each independently an optionally substituted C.sub.3-8 aliphatic group. In certain embodiments, R.sup.a, R.sup.b, R.sup.c, and R.sup.d are each independently an optionally substituted C.sub.3-12 aliphatic group.

(175) In certain embodiments, R.sup.a is an optionally substituted C.sub.1-30 aliphatic group. In certain embodiments, R.sup.b is an optionally substituted C.sub.1-30 aliphatic group. In certain embodiments, R.sup.c is an optionally substituted C.sub.1-30 aliphatic group. In certain embodiments, R.sup.d is an optionally substituted C.sub.1-30 aliphatic group.

(176) In some embodiments, an R.sup.a and an R.sup.b attached to the same carbon are taken together to form one or more optionally substituted 3-12-membered carbocyclic rings. In some embodiments, an R.sup.a and an R.sup.b attached to the same carbon are taken together to form a polycyclic carbocycle comprising two or more optionally substituted 3-8-membered carbocyclic rings. In some embodiments, an R.sup.a and an R.sup.b attached to the same carbon are taken together to form a polycyclic carbocycle comprising two or more optionally substituted 5-7-membered carbocyclic rings.

(177) In some embodiments, an R.sup.a and an R.sup.b attached to the same carbon are taken together to form a bicyclic carbocycle comprising two optionally substituted 3-12-membered carbocyclic rings. In some embodiments, an R.sup.a and an R.sup.b attached to the same carbon are taken together to form a bicyclic carbocycle comprising two optionally substituted 3-8-membered carbocyclic rings. In some embodiments, an R.sup.a and an R.sup.b attached to the same carbon are taken together to form a bicyclic carbocycle comprising two optionally substituted 5-7-membered carbocyclic rings.

(178) In certain embodiments, an R.sup.a and an R.sup.b attached to the same carbon are taken together to form an optionally substituted 3-12-membered carbocyclic ring. In certain embodiments, an R.sup.a and an R.sup.b attached to the same carbon are taken together to form an optionally substituted 3-8-membered carbocyclic ring. In certain embodiments, an R.sup.a and an R.sup.b attached to the same carbon are taken together to form an optionally substituted 5-7-membered carbocyclic ring.

(179) In some embodiments, an R.sup.b and an R.sup.c attached to adjacent carbons are taken together to form one or more optionally substituted 3-12-membered carbocyclic rings. In some embodiments, an R.sup.b and an R.sup.c attached to adjacent carbons are taken together to form a polycyclic carbocycle comprising two or more optionally substituted 3-8-membered carbocyclic rings. In some embodiments, an R.sup.b and an R.sup.c attached to adjacent carbons are taken together to form a polycyclic carbocycle comprising two or more optionally substituted 5-7-membered carbocyclic rings.

(180) In some embodiments, an R.sup.b and an R.sup.c attached to adjacent carbons are taken together to form a bicyclic carbocycle comprising two optionally substituted 3-12-membered carbocyclic rings. In some embodiments, an R.sup.b and an R.sup.c attached to adjacent carbons are taken together to form a bicyclic carbocycle comprising two optionally substituted 3-8-membered carbocyclic rings. In some embodiments, an R.sup.b and an R.sup.c attached to adjacent carbons are taken together to form a bicyclic carbocycle comprising two optionally substituted 5-7-membered carbocyclic rings.

(181) In certain embodiments, an R.sup.b and an R.sup.c attached to adjacent carbons are taken together to form an optionally substituted 3-12-membered carbocyclic ring. In certain embodiments, an R.sup.b and an R.sup.c attached to adjacent carbons are taken together to form an optionally substituted 3-8-membered carbocyclic ring. In certain embodiments, an R.sup.b and an R.sup.c attached to adjacent carbons are taken together to form an optionally substituted 5-7-membered carbocyclic ring.

(182) In certain embodiments, the polymer comprises a copolymer of two different repeating units where R.sup.a, R.sup.b, and R.sup.c of the two different repeating units are not all the same. In some embodiments, a polymer comprises a copolymer of three or more different repeating units wherein R.sup.a, R.sup.b, and R.sup.c of each of the different repeating units are not all the same as R.sup.a, R.sup.b, and R.sup.c of any of the other different repeating units. In some embodiments, a polymer is a random copolymer. In some embodiments, a polymer is a tapered copolymer.

(183) In some embodiments, a polymer contains a metal complex as described herein. In some embodiments, a polymer comprises residue of a metal complex as described herein. In some embodiments, a polymer comprises a salt of an organic cation and X, wherein X is a nucleophile or counterion. In some embodiments, X is 2,4-dinitrophenolate anion.

(184) In some embodiments, R.sup.a is optionally substituted C.sub.1-12 aliphatic. In some embodiments, R.sup.a is optionally substituted C.sub.1-12 heteroaliphatic. In some embodiments, R.sup.a is optionally substituted phenyl. In some embodiments, R.sup.a is optionally substituted 8- to 10-membered aryl. In some embodiments, R.sup.a is optionally substituted 5- to 10-membered heteroaryl. In some embodiments, R.sup.a is optionally substituted 3- to 7-membered heterocyclic.

(185) In certain embodiments, R.sup.a is selected from methyl, ethyl, propyl, butyl, vinyl, allyl, phenyl, trifluoromethyl,

(186) ##STR00257##
or any two or more of the above. In certain embodiments, R.sup.a is methyl. In certain embodiments, R.sup.a is ethyl. In certain embodiments, R.sup.a is propyl. In certain embodiments, R.sup.a is butyl. In certain embodiments, R.sup.a is vinyl. In certain embodiments, R.sup.a is allyl. In certain embodiments, R.sup.a is phenyl. In certain embodiments, R.sup.a is trifluoromethyl. In certain embodiments, R.sup.a is

(187) ##STR00258##
In certain embodiments, R.sup.a is

(188) ##STR00259##
In certain embodiments, R.sup.a is

(189) ##STR00260##
In certain embodiments, R.sup.a is

(190) ##STR00261##
In certain embodiments, R.sup.a is

(191) ##STR00262##
In certain embodiments, R.sup.a is

(192) ##STR00263##
In certain embodiments, R.sup.a is

(193) ##STR00264##

(194) In some embodiments, R.sup.b is hydrogen. In some embodiments, R.sup.b is optionally substituted C.sub.1-12 aliphatic. In some embodiments, R.sup.b is optionally substituted C.sub.1-12 heteroaliphatic. In some embodiments, R.sup.b is optionally substituted phenyl. In some embodiments, R.sup.b is optionally substituted 8- to 10-membered aryl. In some embodiments, R.sup.b is optionally substituted 5- to 10-membered heteroaryl. In some embodiments, R.sup.b is optionally substituted 3- to 7-membered heterocyclic.

(195) In some embodiments, R.sup.c is hydrogen. In some embodiments, R.sup.c is optionally substituted C.sub.1-2 aliphatic. In some embodiments, R.sup.c is optionally substituted C.sub.1-12 heteroaliphatic. In some embodiments, R.sup.c is optionally substituted phenyl. In some embodiments, R.sup.c is optionally substituted 8- to 10-membered aryl. In some embodiments, R.sup.c is optionally substituted 5- to 10-membered heteroaryl. In some embodiments, R.sup.c is optionally substituted 3- to 7-membered heterocyclic.

(196) In some embodiments, R.sup.a and R.sup.c are taken together with intervening atoms to form one or more rings selected from the group consisting of: optionally substituted C.sub.3-C.sub.14 carbocycle, optionally substituted 3- to 14-membered heterocycle, optionally substituted phenyl, optionally substituted C.sub.8-C.sub.10 aryl, and optionally substituted 5- to 10-membered heteroaryl.

(197) In some embodiments, R.sup.b and R.sup.c are taken together with intervening atoms to form one or more rings selected from the group consisting of: optionally substituted C.sub.3-C.sub.14 carbocycle, optionally substituted 3- to 14-membered heterocycle, optionally substituted phenyl, optionally substituted C.sub.8-C.sub.10 aryl, and optionally substituted 5- to 10-membered heteroaryl.

(198) In some embodiments, R.sup.a and R.sup.b are taken together with intervening atoms to form one or more rings selected from the group consisting of: optionally substituted C.sub.3-C.sub.14 carbocycle, optionally substituted 3- to 14-membered heterocycle, optionally substituted phenyl, optionally substituted C.sub.8-C.sub.10 aryl, and optionally substituted 5- to 10-membered heteroaryl.

(199) In some embodiments, the invention includes methods for synthesizing polyol compounds from epoxides. Suitable methods of performing these reactions are disclosed in co-owned PCT Publication No. WO2010/028362 A1, the entire contents of which are hereby incorporated herein by reference.

(200) In some embodiments, the invention includes methods for synthesizing polyethers from epoxides. Suitable methods of performing these reactions are disclosed in U.S. Pat. No. 7,399,822, the entire contents of which are hereby incorporated herein by reference.

(201) In some embodiments, the invention includes methods for synthesizing cyclic carbonates from carbon dioxide and epoxides using complexes described above, suitable methods of performing this reaction are disclosed in U.S. Pat. No. 6,870,004 which is incorporated herein by reference.

EXAMPLES

Example 1

(202) A typical route to asymmetric cobalt (III) cobalt complexes of the present invention is shown in Scheme E1:

(203) ##STR00265##

(204) where R, (Z).sub.m, and X are as defined above and described in classes and subclasses herein.

(205) As shown in Scheme E1, disubstituted salicylaldehyde derivative E1-b is treated with one equivalent of a monohydrochloride salt of 1,2 cyclohexanediamine. The resulting Schiff base E-1b is then contacted with the phenolate anion of a second salicylaldehyde compound E1-a. This provides ligand E1-c which is then treated with a cobalt salt and oxidized in the usual fashion to afford the cobalt III complex E2-e. As will be appreciated by the skilled artisan, numerous variations of the process shown in Scheme E1 are possible. In one variant of this process, an external base is added at the second step rather than relying on the phenolate salt to deprotonate the ammonium salt E-1b. In another variant, an acid is added during the oxidation step such that the X group bound to the cobalt atom in the final catalyst is not the same as the counterion(s) present on the cobalt salt used in the preceding step. In another variant, the metal complex E2-e is treated in additional steps to change the identity of the anion X associated with the cobalt atom and/or those associated with the cationic Z groups. In another variant, the salicylaldehyde E1-a is reacted with the monohydrochloride salt of 1,2 cyclohexanediamine and salicylaldehyde E1-b is added in the subsequent step. In other variants, diamines other than cyclohexanediamine are utilized in the first step. In still other variants, chromium or other metal salts are substituted for the cobalt salt.

(206) Numerous preparations of salicylaldehyde derivatives bearing cationic Z groups are known in the literature: examples include WO 2010/022388; WO 2008/136591, WO 2010/013948, WO 2011/105846 each of which is incorporated herein by reference. The compounds and/or methods disclosed in these references can be used to provide numerous compounds of formula E1-a suitable for the present invention, and any of these compounds can be utilized in the sequence shown in Scheme E1 to provide compounds of the present invention.

(207) While we have described a number of embodiments of this invention, it is apparent that our basic examples may be altered to provide other embodiments that utilize the compounds and methods of this invention. Therefore, it will be appreciated that the scope of this invention is to be defined by the appended claims rather than by the specific embodiments that have been presented by way of example.