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 comprising the step of contacting an epoxide and carbon dioxide with a polymerization catalyst having the structure: ##STR00319## wherein: M is a metal atom; ##STR00320## comprises a multidentate ligand; and (Z).sub.m represents one or more activating moieties tethered to the multidentate ligand, where represents a linker moiety; m represents the number of Z groups present on a linker moiety and is an integer between 1 and 4 inclusive; and each (Z) is an activating functional group independently selected from the group consisting of: ##STR00321## ##STR00322## ##STR00323## ##STR00324## 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 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.4 is hydrogen, hydroxyl, optionally substituted C.sub.1-20 aliphatic; each occurrence of R.sup.5 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 an R.sup.5 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.7 is independently 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, where an R.sup.7 group can be taken with an R.sup.5 group to form one or more optionally substituted rings optionally containing one or more heteroatoms; each occurrence of R.sup.7, is independently 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; and where two R.sup.7 groups 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.7 group can be taken with an R.sup.1 or R.sup.2 group to form one or more optionally substituted rings optionally containing one or more heteroatoms; each occurrence of R.sup.8, R.sup.9, and R.sup.10 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.8, R.sup.9 and R.sup.10 groups can be taken together with intervening atoms to form one or more optionally substituted rings; each occurrence of R.sup.11 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 each occurrence of R.sup.y is independently selected from the group consisting of hydrogen an optionally substituted C.sub.1-6 aliphatic group, and an optionally substituted aryl group, where two or more adjacent R.sup.11 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 is an anion; ring A is an optionally substituted 5- to 10-membered heteroaryl group having 0 to 4 additional heteroatoms independently selected from nitrogen, oxygen, or sulfur; with the provisos that: when Z is ##STR00325## ring A is not an imidazole, an oxazole, or a thiazole; and when ##STR00326## where is CH.sub.2, Z is not ##STR00327##

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

3. The method of claim 1, wherein M is selected from the group consisting of: Co, Al, and Cr.

4. The method of claim 1, wherein M is Co.

5. The method of claim 1, wherein M is Cr.

6. The method of claim 1, wherein M is Al.

7. The method of claim 1, wherein the 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.

8. The method of claim 1, wherein the moiety is 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.

9. The method of claim 1, wherein the moiety is selected from the group consisting of: ##STR00328## ##STR00329## where * represents the site of attachment to the ligand, and each # represents a site of attachment of an activating functional group.

10. The method of claim 1, wherein the ##STR00330## moiety comprises a tetradentate ligand.

11. The method of claim 1, wherein the ##STR00331## moiety comprises two bidentate ligands.

12. The method of claim 10, wherein the tetradentate ligand is selected from the group consisting of salen derivatives, derivatives of salan ligands, bis-2-hydroxybenzamido derivatives, derivatives of the Trost ligand, porphyrin derivatives, derivatives of tetrabenzoporphyrin ligands, derivatives of corrole ligands, phthalocyaninate derivatives, and dibenzotetramethyltetraaza[14]annulene (tmtaa) derivatives.

13. The method of claim 10, wherein the tetradentate ligand is selected from the group consisting of: ##STR00332## ##STR00333## where: R.sup.2a and R.sup.2a, are independently a (Z).sub.m group, hydrogen, 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, R.sup.1a, R.sup.1a, R.sup.3a, and R.sup.3a are independently a (Z).sub.m group, 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, where any of [R.sup.2a and R.sup.3a], [R.sup.2a and R.sup.3a], [R.sup.1a and R.sup.2a], and [R.sup.1a and R.sup.2a] may optionally be taken together with intervening atoms to form one or more rings which may in turn be substituted with one or more R.sup.d groups; R.sup.d at each occurrence is 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; 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.4b is selected from the group consisting of: ##STR00334## where R.sup.c at each occurrence is 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; 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; 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, X is a nuclcophile capable of ring opening an epoxide; Y is a divalent linker selected from the group consisting of: NR, N(R)C(O), C(O)NR, O, C(O), OC(O), C(O)O, S, SO, SO.sub.2, SiR.sub.2, C(S), C(NR), or NN; a polyether; a C.sub.3 to C.sub.8 substituted or unsubstituted carbocycle; and a C.sub.1 to C.sub.8 substituted or unsubstituted heterocycle; m is 0 or an integer from 1 to 6, inclusive; m is 0 or an integer from 1 to 4, inclusive; q is 0 or an integer from 1 to 4, inclusive; and x is 0, 1, or 2.

14. The method of claim 13, wherein ##STR00335## comprises: ##STR00336##

15. The method of claim 14, wherein ##STR00337## comprises: ##STR00338##

16. The method of claim 15, wherein the polymerization catalyst comprises: ##STR00339## wherein: 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, 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 [R.sup.1 and R.sup.4a], [R.sup.1 and R.sup.4a] and any two or more 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 optionally be taken together with intervening atoms to form one or more optionally substituted rings; n is 0 or an integer from 1 to 8, inclusive; and p is 0 or an integer from 1 to 4, inclusive, where at least substituent is a (Z).sub.m group.

17. The method of claim 15, wherein the polymerization catalyst is selected from the group consisting of: ##STR00340##

18. The method of claim 16, wherein the polymerization catalyst is selected from the group consisting of: ##STR00341## ##STR00342## ##STR00343##

19. The method of claim 18, wherein each 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 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.

20. The method of claim 18, wherein each R.sup.4a, R.sup.4a, R.sup.6a, and R.sup.6a is H.

21. The method of claim 18, wherein each R.sup.4a, R.sup.4a, R.sup.6a, and R.sup.6a is H and each R.sup.5a, R.sup.5a, R.sup.7a, and R.sup.7a is independently H, or an optionally substituted C.sub.1-20 aliphatic.

22. The method of claim 16, wherein the polymerization catalyst is selected from the group consisting of ##STR00344## ##STR00345##

23. The method of claim 22, wherein each 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 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.

24. The method of claim 22, wherein each R.sup.4a, R.sup.4a, R.sup.6a, and R.sup.6a is H.

25. The method of claim 22, wherein each R.sup.4a, R.sup.4a, R.sup.6a, and R.sup.6a is H and each R.sup.5a, R.sup.5a, R.sup.7, and R.sup.7a is independently H, or an optionally substituted C.sub.1-20 aliphatic.

26. The method of claim 16, wherein at least one salicylaldehyde-derived portion of the polymerization catalyst is selected from the group consisting of: ##STR00346## ##STR00347##

27. The method of claim 16, wherein at least one salicylaldehyde-derived portion of the polymerization catalyst is selected from the group consisting of: ##STR00348## ##STR00349##

28. The method of claim 16, wherein at least one salicylaldehyde-derived portion of the polymerization catalyst is selected from the group consisting of: ##STR00350## ##STR00351## ##STR00352## ##STR00353##

29. The method of claim 16, wherein at least one salicylaldehyde-derived portion of the polymerization catalyst is selected from the group consisting of: ##STR00354## ##STR00355## ##STR00356## ##STR00357##

30. The method of claim 16, wherein at least one salicylaldehyde-derived portion of the polymerization catalyst is selected from the group consisting of: ##STR00358## ##STR00359## ##STR00360## ##STR00361## ##STR00362##

31. The method of any of claims 26 to 30, wherein one or more Z group is independently a neutral functional group selected from the group consisting of amines, phosphines, gaunidines, bis-guanidines, amidines, and nitrogen-containing heterocycles.

32. The method of any of claims 26 to 30, wherein one or more Z group is a cationic moiety independently selected from the group consisting of: ##STR00363## ##STR00364##

33. The method of any of claims 26 to 33, wherein each linker moiety is independently selected from the group consisting of: ##STR00365## ##STR00366##

34. The method of any of claims 26 to 33, wherein M is selected from the group consisting of cobalt, aluminum, and chromium.

35. The method of any of claims 26 to 33, wherein M is selected from the group consisting of cobalt and chromium.

36. The method of any of claims 26 to 33, wherein M is cobalt.

37. The method of any of claims 26 to 36, wherein X is selected from the group consisting of: chlorine, bromine, an optionally substituted C.sub.1-12 carboxylate, azide, an optionally substituted phenoxide, a sulfonate salt, and a combination of any two or more of these.

38. The method of any of claims 26 to 36, wherein X is selected from the group consisting of chloride, acetate, trifluoroacetate, azide, pentafluorobenzoate, and a nitrophenolate.

39. The method of claim 1, wherein the polymerization catalyst is selected from Table 1.

40. The method of claim 1, wherein the polymerization catalyst contains a total of 1 to 8 Z groups.

41. The method of claim 1, wherein the polymerization catalyst contains a total of 1 to 6 Z groups.

42. The method of claim 1, wherein the polymerization catalyst contains a total of 1 to 4 Z groups.

43. The method of claim 1, wherein the polymerization catalyst contains a total of 2 Z groups.

44. The method of claim 1, wherein the polymerization catalyst contains a total of 4 Z groups.

45. The method of claim 1, wherein at least one Z group is selected from the group consisting of: ##STR00367## ##STR00368##

46. The method of claim 1, wherein at least one Z group is ##STR00369##

47. The method of claim 46, wherein R.sup.1 and R.sup.2 are optionally substituted C.sub.1-20 aliphatic.

48. The method of claim 46, wherein R.sup.1 and R.sup.2 are optionally substituted C.sub.1-10 aliphatic.

49. The method of claim 46, wherein R.sup.1 and R.sup.2 are taken together to form an optionally substituted ring optionally containing additional heteroatoms.

50. The method of claim 1, wherein at least one Z group is selected from the group consisting of: ##STR00370## ##STR00371##

51. The method of claim 1, wherein at least one Z group is selected from the group consisting of: ##STR00372##

52. The method of claim 51, wherein R.sup.1 and R.sup.2 are H or optionally substituted C.sub.1-20 aliphatic.

53. The method of claim 51, wherein R.sup.1 and R.sup.2 are H or optionally substituted C.sub.1-20 aliphatic.

54. The method of claim 51, wherein R.sup.5 is H or optionally substituted C.sub.1-10 aliphatic.

55. The method of claim 51, wherein two or more of R.sup.1, R.sup.2, and R.sup.5 are taken together to form an optionally substituted ring optionally containing additional heteroatoms.

56. The method of claim 1, wherein at least one Z group is selected from the group consisting of: ##STR00373## ##STR00374## ##STR00375##

57. The method of claim 1, wherein at least one Z group is selected from the group consisting of: ##STR00376##

58. The method of claim 57, wherein R.sup.1, R.sup.1, R.sup.1, R.sup.2, R.sup.2, and R.sup.3 and are independently H or optionally substituted C.sub.1-20 aliphatic.

59. The method of claim 57, wherein R.sup.1, R.sup.1, R.sup.1, R.sup.2, R.sup.2, and R.sup.3 are independently H or optionally substituted C.sub.1-10 aliphatic.

60. The method of claim 57, wherein two or more of R.sup.1, R.sup.1, R.sup.1, R.sup.2, R.sup.2, and R.sup.3 are taken together to form one or more optionally substituted rings optionally containing additional heteroatoms.

61. The method of claim 1, wherein at least one Z group is selected from the group consisting of: ##STR00377## ##STR00378##

62. The method of claim 1, wherein at least one Z group is ##STR00379##

63. The method of claim 62, wherein R.sup.1, R.sup.1, R.sup.1, R.sup.2, and R.sup.2 are independently H or optionally substituted C.sub.1-20 aliphatic.

64. The method of claim 62, wherein R.sup.1, R.sup.1, R.sup.1, R.sup.2, and R.sup.2 are independently H or optionally substituted C.sub.1-10 aliphatic.

65. The method of claim 62, wherein two or more of R.sup.1, R.sup.1, R.sup.1, R.sup.2, and R.sup.2 are taken together to form one or more optionally substituted rings optionally containing additional heteroatoms.

66. The method of claim 1, wherein at least one Z group is selected from the group consisting of: ##STR00380##

67. The method of claim 1, wherein at least one Z group is selected from the group consisting of: ##STR00381## ##STR00382##

68. The method of claim 1, wherein the epoxide has the formula: ##STR00383## 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.

69. The method of claim 68, wherein a polymer formed has a formula selected from the group consisting of: ##STR00384##

70. The method of claim 68, wherein R.sup.b, R.sup.c, and R.sup.d are each hydrogen.

71. The method of claim 68, wherein R.sup.a is optionally substituted C.sub.1-12 aliphatic.

72. 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.

73. The method of claim 1, wherein the epoxide is ethylene oxide, propylene oxide, or cyclohexene oxide.

74. The method of claim 1, wherein the epoxide is propylene oxide.

75. The method of claim 1, wherein the CO.sub.2 pressure is between about 50 and 800 psi.

76. The method of claim 1, wherein the ratio of catalyst to epoxide is between about 1:1000 and about 1:100,000.

77. The method of claim 1, further comprising the steps of letting the polymerization proceed until a desired polymer molecular weight has been achieved, quenching the polymerization reaction and isolating the polymer.

78. A polymerization catalyst having the structure: ##STR00385## wherein: M is a metal atom; ##STR00386## comprises a multidentate ligand; and (Z).sub.m represents one or more activating moiety tethered to the multidentate ligand, where represents a linker moiety; m represents the number of Z groups present on a linker moiety and is an integer between 1 and 4 inclusive; and each (Z) is an activating functional group independently selected from the group consisting of: ##STR00387## ##STR00388## ##STR00389## ##STR00390## 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 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.4 is hydrogen, hydroxyl, optionally substituted C.sub.1-20 aliphatic; each occurrence of R.sup.5 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 an R.sup.5 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.7 is independently 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, where an R.sup.7 group can be taken with an R.sup.5 group to form one or more optionally substituted rings optionally containing one or more heteroatoms; each occurrence of R.sup.7, is independently 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; and where two R.sup.7 groups 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.7 group can be taken with an R.sup.1 or R.sup.2 group to form one or more optionally substituted rings optionally containing one or more heteroatoms; each occurrence of R.sup.8, R.sup.9, and R.sup.10 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.8, R.sup.9 and R.sup.10 groups can be taken together with intervening atoms to form one or more optionally substituted rings; each occurrence of R.sup.11 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 each occurrence of R.sup.y is independently selected from the group consisting of hydrogen an optionally substituted C.sub.1-6 aliphatic group, and an optionally substituted aryl group, where two or more adjacent R.sup.11 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 is an anion; ring A is an optionally substituted 5- to 10-membered heteroaryl group having 0 to 4 additional heteroatoms independently selected from nitrogen, oxygen, or sulfur; with the provisos that: when Z is ##STR00391## ring A is not an imidazole, an oxazole, or a thiazole; and when ##STR00392## where is CH.sub.2 Z is not ##STR00393##

79. The polymerization catalyst of claim 78, wherein ##STR00394## comprises: ##STR00395##

80. The polymerization catalyst of claim 79, wherein ##STR00396## comprises: ##STR00397##

81. The polymerization catalyst of claim 80 having a structure selected from the group consisting of: ##STR00398## wherein: R.sup.4a, R.sup.4a, R.sup.5a, R.sup.a, R.sup.6a, R.sup.6a, R.sup.7a, 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, where [R.sup.1 and R.sup.4a], [R.sup.1 and R.sup.4a] and any two or more 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 optionally be taken together with intervening atoms to form one or more optionally substituted rings; n is 0 or an integer from 1 to 8, inclusive; and p is 0 or an integer from 1 to 4, inclusive, where at least substituent is a (Z).sub.m group.

82. The polymerization catalyst of claim 80 having a structure selected from the group consisting of: ##STR00399##

83. The polymerization catalyst of claim 82, having a structure selected from the group consisting of: ##STR00400## ##STR00401## ##STR00402##

84. The polymerization catalyst of claim 83, wherein each 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 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.

85. The polymerization catalyst of claim 83, wherein each R.sup.4a, R.sup.4a, R.sup.6a, and R.sup.6a is H.

86. The polymerization catalyst of claim 83, wherein each R.sup.4a, R.sup.4a, R.sup.6a, and R.sup.6a is H and each R.sup.5a, R.sup.5a, R.sup.7a, and R.sup.7a is independently H, or an optionally substituted C.sub.1-20 aliphatic.

87. The polymerization catalyst of claim 83, wherein the polymerization catalyst is selected from the group consisting of ##STR00403## ##STR00404##

88. The polymerization catalyst of claim 87, wherein each 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 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.

89. The polymerization catalyst of claim 87, wherein each R.sup.4a, R.sup.4a, R.sup.6a, and R.sup.6a is H.

90. The polymerization catalyst of claim 87, wherein each R.sup.4a, R.sup.4a, R.sup.6a, and R.sup.6a is H and each R.sup.5, R.sup.5a, R.sup.7a, and R.sup.7a is independently H, or an optionally substituted C.sub.1-20 aliphatic.

91. The polymerization catalyst of claim 81, wherein at least one salicylaldehyde-derived portion of the polymerization catalyst is selected from the group consisting of: ##STR00405## ##STR00406##

92. The polymerization catalyst of claim 81, wherein at least one salicylaldehyde-derived portion of the polymerization catalyst is selected from the group consisting of: ##STR00407## ##STR00408##

93. The polymerization catalyst of claim 81, wherein at least one salicylaldehyde-derived portion of the polymerization catalyst is selected from the group consisting of: ##STR00409## ##STR00410## ##STR00411## ##STR00412##

94. The polymerization catalyst of claim 81, wherein at least one salicylaldehyde-derived portion of the polymerization catalyst is selected from the group consisting of: ##STR00413## ##STR00414## ##STR00415## ##STR00416##

95. The polymerization catalyst of claim 81, wherein at least one salicylaldehyde-derived portion of the polymerization catalyst is selected from the group consisting of: ##STR00417## ##STR00418## ##STR00419## ##STR00420## ##STR00421##

96. The polymerization catalyst of any of claims 91 to 95, wherein one or more Z group is independently a neutral functional group selected from the group consisting of amines, phosphines, gaunidines, bis-guanidines, amidines, and nitrogen-containing heterocycles.

97. The polymerization catalyst of any of claims 91 to 95, wherein one or more Z group is a cationic moiety independently selected from the group consisting of: ##STR00422## ##STR00423##

98. The polymerization catalyst of any of claims 91 to 95, wherein each linker moiety is independently selected from the group consisting of ##STR00424## ##STR00425##

99. The polymerization catalyst of any of claims 91 to 98, wherein M is selected from the group consisting of cobalt, aluminum, and chromium.

100. The polymerization catalyst of any of claims 91 to 98, wherein M is selected from the group consisting of cobalt and chromium.

101. The polymerization catalyst of any of claims 91 to 98, wherein M is cobalt.

102. The polymerization catalyst of any of claims 91 to 101, wherein X is selected from the group consisting of: chlorine, bromine, an optionally substituted C.sub.1-12 carboxylate, azide, an optionally substituted phenoxide, a sulfonate salt, and a combination of any two or more of these.

103. The polymerization catalyst of claim 83, wherein the catalyst metal complex has a structure selected from those in Table 1.

104. The polymerization catalyst of claim 79, wherein the catalyst has a structure selected from those in Table 1.

105. The polymerization catalyst of claim 79, wherein the catalyst has a structure selected from those in Table 2.

Description

DETAILED DESCRIPTION OF CERTAIN EMBODIMENTS

[0075] The present invention provides, among other things, unimolecular 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-ligand moiety tethered to one or more activating moieties. In some embodiments, an activating moiety comprises a linker and one or more activating functional groups. In some embodiments, provided metal complexes act as polymerization catalysts. In certain embodiments, at least one activating functional group present on the tethered moiety can act as a polymerization co-catalyst and thereby increase the rate of the copolymerization.

[0076] In certain embodiments, provided metal complexes include a metal atom coordinated to a multidentate ligand and at least one activating moiety tethered to the multidentate ligand. In certain embodiments, provided metal complexes have the structure:

##STR00007##

wherein: [0077] M is a metal atom;

##STR00008##

comprises a multidentate ligand; [0078] (Z).sub.m represents one or more activating moieties attached to the multidentate ligand, where is a linker moiety covalently coupled to the ligand, each Z is an activating functional group; and m is an integer from 1 to 4 representing the number of Z groups present on an individual linker moiety.

[0079] In certain embodiments, provided metal complexes include a metal atom coordinated to a multidentate ligand and at least one activating moiety tethered to the multidentate ligand. In some embodiments, there are 1 to 10 activating moieties (Z).sub.m tethered to the multidentate ligand. In certain embodiments, there are 1 to 8 such activating moieties tethered to the multidentate ligand. In certain embodiments, there are 1 to 4 such activating moieties tethered to the multidentate ligand.

I. Activating Functional Groups

[0080] In some embodiments, an activating functional group is selected from the group consisting of neutral nitrogen-containing functional groups, cationic moieties, phosphorous-containing functional groups, and combinations of two or more of these.

I.a. Neutral Nitrogen-Containing Activating Groups

[0081] In some embodiments, one or more tethered activating functional groups on provided metal complexes are neutral nitrogen-containing moieties. In some embodiments, such moieties include one or more of the structures in Table Z-1:

TABLE-US-00001 TABLE Z-1 [00009] [00010] [00011] or a combination of two or more of these,
wherein: [0082] each occurrence of R.sup.1, and R.sup.2 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 two or more R.sup.1 and R.sup.2 groups can be taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more additional heteroatoms; [0083] each occurrence of R.sup.5 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 an R.sup.5 group can be taken with an R.sup.1 or R.sup.2 group to form one or more optionally substituted rings; [0084] each occurrence of R.sup.7 is independently 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;

[0085] In some embodiments, an activating functional group is an N-linked amino

group:

##STR00012## [0086] where R.sup.1 and R.sup.2 are as defined above.

[0087] In certain embodiments, R.sup.1 and R.sup.2 are both hydrogen. In some embodiments, only one of R.sup.1 and R.sup.2 is hydrogen. In certain embodiments, R.sup.1 and R.sup.2 are each independently an optionally substituted radical selected from the group consisting of C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic, 5- to 14-membered heteroaryl, phenyl, 8- to 10-membered aryl and 3- to 7-membered heterocyclic. In certain embodiments, R.sup.1 and R.sup.2 are each independently an optionally substituted radical 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.

[0088] In certain embodiments, R.sup.1 and R.sup.2 are each independently an optionally substituted radical selected from the group consisting of C.sub.1-12 aliphatic and C.sub.1-12 heteroaliphatic. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted C.sub.1-20 aliphatic. In some embodiments, R.sup.1 and R.sup.2 are each independently optionally substituted C.sub.1-12 aliphatic. In some embodiments, R.sup.1 and R.sup.2 are each independently optionally substituted C.sub.1-6 aliphatic. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted C.sub.1-20 heteroaliphatic. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted C.sub.1-12 heteroaliphatic. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted phenyl. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted 8- to 10-membered aryl. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted phenyl group. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted 5- to 10-membered heteroaryl group. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted 3- to 7-membered heterocyclic.

[0089] In certain embodiments, R.sup.1 and R.sup.2 are each independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, optionally substituted phenyl, or optionally substituted benzyl. In certain embodiments, R.sup.1 and R.sup.2 are both methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl or benzyl. In some embodiments, R.sup.1 and R.sup.2 are each butyl. In some embodiments, R.sup.1 and R.sup.2 are each isopropyl. In some embodiments, R.sup.1 and R.sup.2 are perfluoro. In some embodiments, R.sup.1 and R.sup.2 are CF.sub.2CF.sub.3. In some embodiments, R.sup.1 and R.sup.2 are each phenyl. In some embodiments, R.sup.1 and R.sup.2 are each benzyl.

[0090] In some embodiments, R.sup.1 and R.sup.2 are taken together with intervening atoms to form one or more optionally substituted rings. In certain embodiments, R.sup.1 and R.sup.2 are taken together to form a ring fragment selected from the group consisting of: C(R.sup.y).sub.2, C(R.sup.y).sub.2C(R.sup.y).sub.2, C(R.sup.y).sub.2C(R.sup.y).sub.2C(R.sup.y).sub.2, C(R.sup.y).sub.2OC(R.sup.y).sub.2, and C(R.sup.y).sub.2NR.sup.yC(R.sup.y).sub.2. In certain embodiments, R.sup.1 and R.sup.2 are taken together to form a ring fragment selected from the group consisting of: CH.sub.2, CH.sub.2CH.sub.2, CH.sub.2CH.sub.2CH.sub.2, CH.sub.2OCH.sub.2, and CH.sub.2NR.sup.yCH.sub.2. In some embodiments, R.sup.1 and R.sup.2 are taken together to form an unsaturated linker moiety optionally containing one or more additional heteroatoms. In some embodiments, the resulting nitrogen-containing ring is partially unsaturated. In certain embodiments, the resulting nitrogen-containing ring comprises a fused polycyclic heterocycle.

[0091] In specific embodiments, an N-linked amine activating functional group is selected from the group consisting of:

##STR00013## ##STR00014##

[0092] In some embodiments, one or more activating functional groups is an N-linked

hydroxyl amine derivative:

##STR00015## [0093] wherein R.sup.1 and R.sup.7 are as defined above.

[0094] In certain embodiments, R.sup.7 is hydrogen. In some embodiments, R.sup.7 is an optionally substituted radical selected from the group consisting of C.sub.1-12 aliphatic, phenyl, 8- to 10-membered aryl, and 3- to 7-membered heterocyclic. In certain embodiments, R.sup.7 is a C.sub.1-12 aliphatic. In certain embodiments, R.sup.7 is a C.sub.1-6 aliphatic. In some embodiments, R.sup.7 is an optionally substituted 8- to 1-membered aryl group. In certain embodiments, R.sup.7 is an optionally substituted phenyl. In some embodiments, R.sup.7 is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl or benzyl.

[0095] In certain embodiments, R.sup.1 is hydrogen. In some embodiments, R.sup.1 is an optionally substituted radical selected from the group consisting of C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic, 5- to 14-membered heteroaryl, phenyl, 8- to 10-membered aryl and 3- to 7-membered heterocyclic. In some embodiments, R.sup.1 is an optionally substituted radical 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.

[0096] In some embodiments, R.sup.1 is an optionally substituted radical selected from the group consisting of C-1.sub.2 aliphatic and C.sub.1-12 heteroaliphatic. In some embodiments, R.sup.1 is an optionally substituted C.sub.1-20 aliphatic. In certain embodiments, R.sup.1 is an optionally substituted C.sub.1-12 aliphatic. In some embodiments, R.sup.1 is an optionally substituted C.sub.1-6 aliphatic. In some embodiments, R.sup.1 is an optionally substituted C.sub.1-12 heteroaliphatic. In some embodiments, R.sup.1 is an optionally substituted 8- to 10-membered aryl. In certain embodiments, R.sup.1 is an optionally substituted phenyl. In some embodiments, R.sup.1 is an optionally substituted 5- to 10-membered heteroaryl. In some embodiments, R.sup.1 is an optionally substituted 3- to 7-membered heterocyclic.

[0097] In certain embodiments, R.sup.1 is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl or benzyl. In some embodiments, R.sup.1 is butyl. In some embodiments, R.sup.1 is isopropyl. In some embodiments, R.sup.1 is phenyl. In some embodiments, R.sup.1 is benzyl. In some embodiments, R.sup.1 is perfluoro. In some embodiments, R.sup.1 is CF.sub.2CF.sub.3. In certain embodiments, R.sup.1 and R.sup.7 are taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more additional heteroatoms.

[0098] In certain embodiments, one or more N-linked hydroxyl amine activating functional groups are selected from the group consisting of:

##STR00016##

[0099] In some embodiments, an activating functional group in a provided metal complexis an amidine. In certain embodiments, such amidine activating functional groups are selected from:

##STR00017## [0100] where each occurrence of R.sup.1, R.sup.2 and R.sup.5 are as defined above.

[0101] In certain embodiments, each R.sup.1 and R.sup.2 is hydrogen. In some embodiments, only one of R.sup.1 and R.sup.2 is hydrogen. In certain embodiments, each R.sup.1 and R.sup.2 is independently an optionally substituted radical selected from the group consisting of C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic, 5- to 14-membered heteroaryl, phenyl, 8- to 10-membered aryl and 3- to 7-membered heterocyclic. In some embodiments, each R.sup.1 and R.sup.2 is independently an optionally substituted radical 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.

[0102] In certain embodiments, R.sup.1 and R.sup.2 are each independently an optionally substituted radical selected from the group consisting of C.sub.1-12 aliphatic and C.sub.1-12 heteroaliphatic. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted C.sub.1-20 aliphatic. In some embodiments, R.sup.1 and R.sup.2 are each independently optionally substituted C.sub.1-12 aliphatic. In some embodiments, R.sup.1 and R.sup.2 are each independently optionally substituted C.sub.1-6 aliphatic. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted C.sub.1-20 heteroaliphatic. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted C.sub.1-12 heteroaliphatic. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted 8- to 10-membered aryl. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted phenyl group. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted 5- to 10-membered heteroaryl group. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted 3- to 7-membered heterocyclic.

[0103] In certain embodiments, R.sup.1 and R.sup.2 are each independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, optionally substituted phenyl, or optionally substituted benzyl. In certain embodiments, R.sup.1 and R.sup.2 are both methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl or benzyl. In some embodiments, R.sup.1 and R.sup.2 are each butyl. In some embodiments, R.sup.1 and R.sup.2 are each isopropyl. In some embodiments, R.sup.1 and R.sup.2 are perfluoro. In some embodiments, R.sup.1 and R.sup.2 are CF.sub.2CF.sub.3. In some embodiments, R.sup.1 and R.sup.2 are each phenyl. In some embodiments, R.sup.1 and R.sup.2 are each benzyl.

[0104] In some embodiments, R.sup.1 and R.sup.2 are taken together with intervening atoms to form one or more optionally substituted rings. In certain embodiments, R.sup.1 and R.sup.2 are taken together to form a ring fragment selected from the group consisting of: C(R.sup.y).sub.2, C(R.sup.y).sub.2C(R.sup.y).sub.2, C(R.sup.y).sub.2C(R.sup.y).sub.2C(R.sup.y).sub.2, C(R.sup.y).sub.2OC(R.sup.y).sub.2, and C(R.sup.y).sub.2NR.sup.yC(R.sup.y).sub.2. In certain embodiments, R.sup.1 and R.sup.2 are taken together to form a ring fragment selected from the group consisting of: CH.sub.2, CH.sub.2CH.sub.2, CH.sub.2CH.sub.2CH.sub.2, CH.sub.2OCH.sub.2, and CH.sub.2NR.sup.yCH.sub.2. In some embodiments, R.sup.1 and R.sup.2 are taken together to form an unsaturated linker moiety optionally containing one or more additional heteroatoms. In some embodiments, the resulting nitrogen-containing ring is partially unsaturated. In certain embodiments, the resulting nitrogen-containing ring comprises a fused polycyclic heterocycle.

[0105] In certain embodiments, R.sup.5 is H. In certain embodiments, R.sup.5 is optionally substituted C.sub.1-20 aliphatic. In some embodiments, R.sup.5 is optionally substituted 6- to 14-membered aryl. In certain embodiments, R.sup.5 is optionally substituted C.sub.1-12 aliphatic. In some embodiments, R.sup.5 is optionally substituted C.sub.1-6 aliphatic. In certain embodiments, R.sup.5 is optionally substituted phenyl.

[0106] In some embodiments, one or more R.sup.1 or R.sup.2 groups are taken together with R.sup.5 and intervening atoms to form an optionally substituted ring. In certain embodiments, R.sup.1 and R.sup.5 are taken together to form an optionally substituted 5- or 6-membered ring. In some embodiments, R.sup.2 and R.sup.5 are taken together to form an optionally substituted 5- or 6-membered ring optionally containing one or more additional heteroatoms. In some embodiments, R.sup.1, R.sup.2 and R.sup.5 are taken together to form an optionally substituted fused ring system. In some embodiments such rings formed by combinations of any of R.sup.1, R.sup.2 and R.sup.5 are partially unsaturated or aromatic.

[0107] In certain embodiments, an activating functional group is an N-linked amidine:

##STR00018##

In certain embodiments, N-linked amidine groups are selected from the group consisting of:

##STR00019##

[0108] In certain embodiments, activating functional groups are amidine moieties linked through the imine nitrogen:

##STR00020##

[0109] In certain embodiments, imine-linked amidine activating functional groups are selected from the group consisting of:

##STR00021##

[0110] In certain embodiments, activating functional groups are amidine moieties linked through a carbon atom:

##STR00022##

In certain embodiments, carbon-linked amidine activating groups are selected from the group consisting of:

##STR00023## ##STR00024##

[0111] In some embodiments, one or more activating functional groups is a carbamate. In certain embodiments, a carbamate is N-linked:

##STR00025##

where R.sup.1 and R.sup.2 are as defined above. In some embodiments, a carbamate is O-linked:

##STR00026##

where R.sup.1 and R.sup.2 are as defined above.

[0112] In certain embodiments, R.sup.1 and R.sup.2 are both hydrogen. In some embodiments, only one of R.sup.1 and R.sup.2 is hydrogen. In certain embodiments, R.sup.1 and R.sup.2 are each independently an optionally substituted radical selected from the group consisting of C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic, 5- to 14-membered heteroaryl, phenyl, 8- to 10-membered aryl and 3- to 7-membered heterocyclic. In some embodiments, R.sup.1 and R.sup.2 are each independently an optionally substituted radical 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.

[0113] In certain embodiments, R.sup.1 and R.sup.2 are each independently an optionally substituted radical selected from the group consisting of C.sub.1-12 aliphatic and C.sub.1-12 heteroaliphatic. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted C.sub.1-20 aliphatic. In some embodiments, R.sup.1 and R.sup.2 are each independently optionally substituted C.sub.1-12 aliphatic. In some embodiments, R.sup.1 and R.sup.2 are each independently optionally substituted C.sub.1-6 aliphatic. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted C.sub.1-20 heteroaliphatic. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted C.sub.1-12 heteroaliphatic. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted 8- to 10-membered aryl. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted phenyl group. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted 5- to 10-membered heteroaryl group. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted 3- to 7-membered heterocyclic.

[0114] In certain embodiments, R.sup.1 and R.sup.2 are each independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, optionally substituted phenyl, or optionally substituted benzyl. In certain embodiments, R.sup.1 and R.sup.2 are both methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl or benzyl. In some embodiments, R.sup.1 and R.sup.2 are each butyl. In some embodiments, R.sup.1 and R.sup.2 are each isopropyl. In some embodiments, R.sup.1 and R.sup.2 are perfluoro. In some embodiments, R.sup.1 and R.sup.2 are CF.sub.2CF.sub.3. In some embodiments, R.sup.1 and R.sup.2 are each phenyl. In some embodiments, R.sup.1 and R.sup.2 are each benzyl.

[0115] In some embodiments, R.sup.1 and R.sup.2 are taken together with intervening atoms to form one or more optionally substituted rings. In certain embodiments, R.sup.1 and R.sup.2 are taken together to form a ring fragment selected from the group consisting of: C(R.sup.y).sub.2, C(R.sup.y).sub.2C(R.sup.y).sub.2, C(R.sup.y).sub.2C(R.sup.y).sub.2C(R.sup.y).sub.2, C(R.sup.y).sub.2OC(R.sup.y).sub.2, and C(R.sup.y).sub.2NR.sup.yC(R.sup.y).sub.2. In certain embodiments, R.sup.1 and R.sup.2 are taken together to form a ring fragment selected from the group consisting of: CH.sub.2, CH.sub.2CH.sub.2, CH.sub.2CH.sub.2CH.sub.2, CH.sub.2OCH.sub.2, and CH.sub.2NR.sup.yCH.sub.2. In some embodiments, R.sup.1 and R.sup.2 are taken together to form an unsaturated linker moiety optionally containing one or more additional heteroatoms. In some embodiments, the resulting nitrogen-containing ring is partially unsaturated. In certain embodiments, the resulting nitrogen-containing ring comprises a fused polycyclic heterocycle. In some embodiments, R.sup.2 is selected from the group consisting of: methyl, t-butyl, t-amyl, benzyl, adamantyl, allyl, 4-methoxycarbonylphenyl, 2-(methylsulfonyl)ethyl, 2-(4-biphenylyl)-prop-2-yl, 2-(trimethylsilyl)ethyl, 2-bromoethyl, and 9-fluorenylmethyl.

[0116] In some embodiments, an activating functional group is a guanidine or bis-guanidine group:

##STR00027## [0117] where each occurrence of R.sup.1, R.sup.1, R.sup.2, R.sup.2, R.sup.2, R.sup.3, 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.1, R.sup.2, R.sup.2, R.sup.2, R.sup.3, 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;

[0118] In certain embodiments, each occurrence of R.sup.1, R.sup.1, R.sup.2, R.sup.2, R.sup.2, R.sup.3, and R.sup.3 is hydrogen. In some embodiments, each occurrence of R.sup.1, R.sup.1, R.sup.2, R.sup.2, R.sup.2, R.sup.3, and R.sup.3, is hydrogen or an optionally substituted radical selected from the group consisting of C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic; 3- to 7-membered heterocyclic, phenyl, and 8- to 10-membered aryl. In some embodiments, each occurrence of R.sup.1, R.sup.1, R.sup.2, R.sup.2, R.sup.2, R.sup.3, and R.sup.3 is hydrogen or an optionally substituted radical 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. In certain embodiments, each occurrence of R.sup.1, R.sup.1, R.sup.2, R.sup.2, R.sup.2, R.sup.3, and R.sup.3 is independently hydrogen or an optionally substituted radical selected from the group consisting of C.sub.1-20 aliphatic, phenyl, and 8- to 10-membered aryl. In certain embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally hydrogen or an optionally substituted C.sub.1-8 aliphatic, phenyl, or 8- to 10-membered aryl group. In some embodiments, each occurrence of R.sup.1, R.sup.1, R.sup.2, R.sup.2, R.sup.2, R.sup.3, and R.sup.3 is independently hydrogen or an optionally substituted C.sub.1-20 aliphatic. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently hydrogen an optionally substituted aryl group or an optionally substituted C.sub.1-8 aliphatic group. In some embodiments, each occurrence of R.sup.1, R.sup.1, R.sup.2, R.sup.2, R.sup.2, R.sup.3, and R.sup.3 is independently hydrogen or an optionally substituted C.sub.1-6 aliphatic group. In some embodiments, each occurrence of R.sup.1, R.sup.1, R.sup.2, R.sup.2, R.sup.2, R.sup.3, and R.sup.3 is independently hydrogen or an optionally substituted C.sub.1-4 aliphatic group. In some embodiments, each occurrence of R.sup.1, R.sup.1, R.sup.2, R.sup.2, R.sup.2, R.sup.3, and R.sup.3 is independently an optionally substituted C.sub.1-20 aliphatic. In some embodiments, R.sup.1, R.sup.1, R.sup.2, R.sup.2, R.sup.2, R.sup.3, and R.sup.3 are each independently optionally substituted C.sub.1-12 aliphatic. In some embodiments, R.sup.1, R.sup.1, R.sup.2, R.sup.2, R.sup.2, R.sup.3, and R.sup.3 are each independently optionally substituted C.sub.1-6 aliphatic. In some embodiments, one or more occurrence of R.sup.1, R.sup.2, R.sup.2, R.sup.2, R.sup.3, and R.sup.3 is independently an optionally substituted C.sub.1-20 heteroaliphatic. In some embodiments, one or more occurrence of R.sup.1, R.sup.1, R.sup.2, R.sup.2, R.sup.2, R.sup.3, and R.sup.3 is independently hydrogen or an optionally substituted phenyl or 8- to 10-membered aryl. In some embodiments, one or more occurrence of R.sup.1, R.sup.1, R.sup.2, R.sup.2, R.sup.2, R.sup.3, and R.sup.3 is independently hydrogen, or an optionally substituted 5- to 10-membered heteroaryl.

[0119] In some embodiments, R.sup.1 is optionally substituted C.sub.1-6 aliphatic. In certain embodiments, R.sup.1 is optionally substituted C.sub.1-6 aliphatic. In certain embodiments, R.sup.2 is optionally substituted C.sub.1-6 aliphatic. In certain embodiments, R.sup.2 is optionally substituted C.sub.1-6 aliphatic. In certain embodiments, R.sup.2 is optionally substituted C.sub.1-6 aliphatic. In certain embodiments, R.sup.3 is optionally substituted C.sub.1-6 aliphatic. In certain embodiments, R.sup.3 is optionally substituted C.sub.1-6 aliphatic. In some embodiments, each occurrence of R.sup.1, R.sup.1, R.sup.2, R.sup.2, R.sup.2, R.sup.3, and R.sup.3 is independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl or benzyl. In certain embodiments, R.sup.1, R.sup.1, R.sup.2, R.sup.2, R.sup.2, R.sup.3, and R.sup.3 are each methyl or ethyl. In some embodiments, one or more R.sup.1, R.sup.1, R.sup.2, R.sup.2, R.sup.2, R.sup.3, and R.sup.3 is perfluoro.

[0120] In some embodiments, any two or more R.sup.1, R.sup.1, R.sup.2, R.sup.2, R.sup.2, R.sup.3, and R.sup.3 groups are taken together with intervening atoms to form one or more optionally substituted rings.

[0121] In certain embodiments, R.sup.1 and R.sup.2 are taken together with intervening atoms to form an optionally substituted ring optionally containing one or more additional heteroatoms. In some embodiments, R.sup.2 and R.sup.2 are taken together with intervening atoms to form an optionally substituted ring optionally containing one or more additional heteroatoms. In certain embodiments, R.sup.1 and R.sup.3 are taken together with intervening atoms to form an optionally substituted ring optionally containing one or more additional heteroatoms. In some embodiments, [R.sup.2 and R.sup.2] and [R.sup.1 and R.sup.3] are taken together with intervening atoms to form an optionally substituted ring optionally containing one or more additional heteroatoms. In some embodiments, three or more R.sup.1, R.sup.1, R.sup.2, R.sup.2, R.sup.2, R.sup.3, and R.sup.3 groups are taken together with any intervening atoms to form optionally substituted 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.2groups are taken together to form an optionally substituted fused ring system.

[0122] In certain embodiments where an activating functional group is a guanidine or bis guanidine moiety, it is chosen from the group consisting of:

##STR00028## ##STR00029##

[0123] In some embodiments, an activating functional group is a urea:

##STR00030##

where R.sup.1, and R.sup.2 are as defined above.

[0124] In certain embodiments, R.sup.1 and R.sup.2 are each hydrogen. In some embodiments, only one of R.sup.1 and R.sup.2 is hydrogen. In certain embodiments, R.sup.1 and R.sup.2 are each independently 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.

[0125] In certain embodiments, R.sup.1 and R.sup.2 are each independently an optionally substituted radical selected from the group consisting of C.sub.1-12 aliphatic and C.sub.1-12 heteroaliphatic. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted C.sub.1-20 aliphatic. In some embodiments, R.sup.1 and R.sup.2 are each independently optionally substituted C.sub.1-12 aliphatic. In some embodiments, R.sup.1 and R.sup.2 are each independently optionally substituted C.sub.1-6 aliphatic. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted C.sub.1-20 heteroaliphatic. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted C.sub.1-12 heteroaliphatic. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted 8- to 10-membered aryl. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted phenyl group. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted 5- to 10-membered heteroaryl group. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted 3- to 7-membered heterocyclic.

[0126] In certain embodiments, R.sup.1 and R.sup.2 are each independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, optionally substituted phenyl, or optionally substituted benzyl. In certain embodiments, R.sup.1 and R.sup.2 are both methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl or benzyl. In some embodiments, R.sup.1 and R.sup.2 are each butyl. In some embodiments, R.sup.1 and R.sup.2 are each isopropyl. In some embodiments, R.sup.1 and R.sup.2 are perfluoro. In some embodiments, R.sup.1 and R.sup.2 are CF.sub.2CF.sub.3. In some embodiments, R.sup.1 and R.sup.2 are each phenyl. In some embodiments, R.sup.1 and R.sup.2 are each benzyl.

[0127] In some embodiments, R.sup.1 and R.sup.2 are taken together with intervening atoms to form one or more optionally substituted rings. In certain embodiments, R.sup.1 and R.sup.2 are taken together to form a ring fragment selected from the group consisting of: C(R.sup.y).sub.2, C(R.sup.y).sub.2C(R.sup.y).sub.2, C(R.sup.y).sub.2C(R.sup.y).sub.2C(R.sup.y).sub.2, C(R.sup.y).sub.2OC(R.sup.y).sub.2, and C(R.sup.y).sub.2NR.sup.yC(R.sup.y).sub.2. In certain embodiments, R.sup.1 and R.sup.2 are taken together to form a ring fragment selected from the group consisting of: CH.sub.2, CH.sub.2CH.sub.2, CH.sub.2CH.sub.2CH.sub.2, CH.sub.2OCH.sub.2, and CH.sub.2NR.sup.yCH.sub.2. In some embodiments, R.sup.1 and R.sup.2 are taken together to form an unsaturated linker moiety optionally containing one or more additional heteroatoms. In some embodiments, the resulting nitrogen-containing ring is partially unsaturated. In certain embodiments, the resulting nitrogen-containing ring comprises a fused polycyclic heterocycle.

[0128] In certain embodiments, activating functional groups are oxime or hydrazone groups:

##STR00031## [0129] where R.sup.1, R.sup.2, R.sup.5, and R.sup.7 are as defined above.

[0130] In certain embodiments, R.sup.1 and R.sup.2 are both hydrogen. In some embodiments, only one of R.sup.1 and R.sup.2 is hydrogen. In certain embodiments, R.sup.1 and R.sup.2 are each independently an optionally substituted radical selected from the group consisting of C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic, 5- to 14-membered heteroaryl, 8- to 10-membered aryl and 3- to 7-membered heterocyclic. In certain embodiments, R.sup.1 and R.sup.2 are each independently an optionally substituted radical 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.

[0131] In certain embodiments, R.sup.1 and R.sup.2 are each independently an optionally substituted radical selected from the group consisting of C.sub.1-12 aliphatic and C.sub.1-12 heteroaliphatic. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted C.sub.1-20 aliphatic. In some embodiments, R.sup.1 and R.sup.2 are each independently optionally substituted C.sub.1-12 aliphatic. In some embodiments, R.sup.1 and R.sup.2 are each independently optionally substituted C.sub.1-6 aliphatic. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted C.sub.1-20 heteroaliphatic. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted C.sub.1-12 heteroaliphatic. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted 8- to 10-membered aryl. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted phenyl group. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted 5- to 10-membered heteroaryl group. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted 3- to 7-membered heterocyclic.

[0132] In certain embodiments, R.sup.1 and R.sup.2 are each independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, optionally substituted phenyl, or optionally substituted benzyl. In certain embodiments, R.sup.1 and R.sup.2 are both methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl or benzyl. In some embodiments, R.sup.1 and R.sup.2 are each butyl. In some embodiments, R.sup.1 and R.sup.2 are each isopropyl. In some embodiments, R.sup.1 and R.sup.2 are perfluoro. In some embodiments, R.sup.1 and R.sup.2 are CF.sub.2CF.sub.3. In some embodiments, R.sup.1 and R.sup.2 are each phenyl. In some embodiments, R.sup.1 and R.sup.2 are each benzyl.

[0133] In some embodiments, R.sup.1 and R.sup.2 are taken together with intervening atoms to form one or more optionally substituted rings. In certain embodiments, R.sup.1 and R.sup.2 are taken together to form a ring fragment selected from the group consisting of: C(R.sup.y).sub.2, C(R.sup.y).sub.2C(R.sup.y).sub.2, C(R.sup.y).sub.2C(R.sup.y).sub.2C(R.sup.y).sub.2, C(R.sup.y).sub.2OC(R.sup.y).sub.2, and C(R.sup.y).sub.2NR.sup.yC(R.sup.y).sub.2. In certain embodiments, R.sup.1 and R.sup.2 are taken together to form a ring fragment selected from the group consisting of: CH.sub.2, CH.sub.2CH.sub.2, CH.sub.2CH.sub.2CH.sub.2, CH.sub.2OCH.sub.2, and CH.sub.2NR.sup.yCH.sub.2. In some embodiments, R.sup.1 and R.sup.2 are taken together to form an unsaturated linker moiety optionally containing one or more additional heteroatoms. In some embodiments, the resulting nitrogen-containing ring is partially unsaturated. In certain embodiments, the resulting nitrogen-containing ring comprises a fused polycyclic heterocycle.

[0134] In certain embodiments, R.sup.5 is H. In certain embodiments, R.sup.5 is optionally substituted C.sub.1-20 aliphatic, and in some embodiments R.sup.5 is optionally substituted 6- to 14-membered aryl. In certain embodiments, R.sup.5 is optionally substituted C.sub.1-12 aliphatic and in some embodiments, optionally substituted C.sub.1-6 aliphatic. In certain embodiments, R.sup.5 is optionally substituted phenyl.

[0135] In some embodiments, one or more R.sup.1 or R.sup.2 groups are taken together with R.sup.5 and intervening atoms to form an optionally substituted ring. In certain embodiments, R.sup.1 and R.sup.5 are taken together to form an optionally substituted 5- or 6-membered ring. In some embodiments, R.sup.2 and R.sup.5 are taken together to form an optionally substituted 5- or 6-membered ring optionally containing one or more additional heteroatoms. In some embodiments, R.sup.1, R.sup.2 and R.sup.5 are taken together to form an optionally substituted fused ring system. In some embodiments such rings formed by combinations of any of R.sup.1, R.sup.2 and R.sup.5 are partially unsaturated or aromatic.

[0136] In certain embodiments, R.sup.7 is H. In certain embodiments, R.sup.7 is optionally substituted C.sub.1-20 aliphatic, while in some embodiments R.sup.5 is optionally substituted 6- to 14-membered aryl. In certain embodiments, R.sup.7 is optionally substituted C.sub.1-12 aliphatic or in some embodiments, optionally substituted C.sub.1-6 aliphatic. In certain embodiments, R.sup.7 is optionally substituted C.sub.1-12 acyl or in some embodiments, optionally substituted C.sub.1-6 acyl. In certain embodiments, R.sup.7 is optionally substituted phenyl. In some embodiments, R.sup.7 is a hydroxyl protecting group. In some embodiments, R.sup.7 is a silyl protecting group.

[0137] In some embodiments, an activating functional group is an N-oxide derivative:

##STR00032##

where R.sup.1 and R.sup.2 are as defined above.

[0138] In certain embodiments, R.sup.1 and R.sup.2 are both hydrogen. In some embodiments, only one of R.sup.1 and R.sup.2 is hydrogen. In certain embodiments, R.sup.1 and R.sup.2 are each independently an optionally substituted radical selected from the group consisting of C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic, 5- to 14-membered heteroaryl, phenyl, or 8- to 10-membered aryl and 3- to 7-membered heterocyclic.

[0139] In certain embodiments, R.sup.1 and R.sup.2 are each independently an optionally substituted radical selected from the group consisting of C.sub.1-12 aliphatic and C.sub.1-12 heteroaliphatic. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted C.sub.1-20 aliphatic. In some embodiments, R.sup.1 and R.sup.2 are each independently optionally substituted C.sub.1-12 aliphatic. In some embodiments, R.sup.1 and R.sup.2 are each independently optionally substituted C.sub.1-6 aliphatic. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted C.sub.1-20 heteroaliphatic. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted C.sub.1-12 heteroaliphatic. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted 8- to 10-membered aryl. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted phenyl group. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted 5- to 10-membered heteroaryl group. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted 3- to 7-membered heterocyclic.

[0140] In certain embodiments, R.sup.1 and R.sup.2 are each independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, optionally substituted phenyl, or optionally substituted benzyl. In certain embodiments, R.sup.1 and R.sup.2 are both methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl or benzyl. In some embodiments, R and R.sup.2 are each butyl. In some embodiments, R.sup.1 and R.sup.2 are each isopropyl. In some embodiments, R.sup.1 and R.sup.2 are perfluoro. In some embodiments, R.sup.1 and R.sup.2 are CF.sub.2CF.sub.3. In some embodiments, R.sup.1 and R.sup.2 are each phenyl. In some embodiments, R.sup.1 and R.sup.2 are each benzyl.

[0141] In some embodiments, R.sup.1 and R.sup.2 are taken together with intervening atoms to form one or more optionally substituted rings. In certain embodiments, R.sup.1 and R.sup.2 are taken together to form a ring fragment selected from the group consisting of: C(R.sup.y).sub.2, C(R.sup.y).sub.2C(R.sup.y).sub.2, C(R.sup.y).sub.2C(R.sup.y).sub.2C(R.sup.y).sub.2, C(R.sup.y).sub.2OC(R.sup.y).sub.2, and C(R.sup.y).sub.2NR.sup.yC(R.sup.y).sub.2. In certain embodiments, R.sup.1 and R.sup.2 are taken together to form a ring fragment selected from the group consisting of: CH.sub.2, CH.sub.2CH.sub.2, CH.sub.2CH.sub.2CH.sub.2, CH.sub.2OCH.sub.2, and CH.sub.2NR.sup.yCH.sub.2. In some embodiments, R.sup.1 and R.sup.2 are taken together to form an unsaturated linker moiety optionally containing one or more additional heteroatoms. In some embodiments, the resulting nitrogen-containing ring is partially unsaturated. In certain embodiments, the resulting nitrogen-containing ring comprises a fused polycyclic heterocycle.

[0142] In specific embodiments, an N-oxide activating functional group is selected from the group consisting of:

##STR00033## ##STR00034##

I.b. Cationic Activating Groups

[0143] In some embodiments, one or more tethered activating functional groups on provided metal complexes are cationic moieties include cationic moieties. In some embodiments, such moieties include one or more of the structures in Table Z-2:

TABLE-US-00002 TABLE Z-2 [00035] [00036] [00037] [00038] [00039] [00040] [00041] or a combination of two or more of these,
wherein: [0144] each occurrence of R.sup.1, R.sup.2, and R.sup.3 is as previously defined; [0145] R.sup.4 is hydrogen, hydroxyl, optionally substituted C.sub.1-20 aliphatic; [0146] each occurrence of R.sup.5 and R.sup.6 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 R.sup.5 and R.sup.6 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.5 or R.sup.6 group can be taken with an R.sup.1 or R.sup.2 group to form one or more optionally substituted rings; [0147] each occurrence of R.sup.8, R.sup.9, and R.sup.10 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.8, R.sup.9 and R.sup.10 groups can be taken together with intervening atoms to form one or more optionally substituted rings; [0148] each occurrence of R.sup.11 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 each occurrence of R.sup.y is independently hydrogen or an optionally substituted C.sub.1-6 aliphatic group, and where two or more adjacent R.sup.11 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; [0149] X.sup. is any anion, and [0150] Ring A is an optionally substituted, 5- to 10-membered heteroaryl group.

[0151] In certain embodiments, a cationic activating functional group is a protonated amine:

##STR00042##

where R.sup.1 and R.sup.2 are as defined above.

[0152] In certain embodiments, R.sup.1 and R.sup.2 are both hydrogen. In some embodiments, only one of R.sup.1 and R.sup.2 is hydrogen. In certain embodiments, R.sup.1 and R.sup.2 are each independently an optionally substituted radical selected from the group consisting of C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic, 5- to 14-membered heteroaryl, phenyl, or 8- to 10-membered aryl and 3- to 7-membered heterocyclic. In certain embodiments, R.sup.1 and R.sup.2 are each independently an optionally substituted radical 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.

[0153] In certain embodiments, R.sup.1 and R.sup.2 are each independently an optionally substituted radical selected from the group consisting of C.sub.1-12 aliphatic and C.sub.1-12 heteroaliphatic. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted C.sub.1-20 aliphatic. In some embodiments, R.sup.1 and R.sup.2 are each independently optionally substituted C.sub.1-12 aliphatic. In some embodiments, R.sup.1 and R.sup.2 are each independently optionally substituted C.sub.1-6 aliphatic. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted C.sub.1 2.sub.0 heteroaliphatic. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted C.sub.1-12 heteroaliphatic. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted 8- to 10-membered aryl. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted phenyl group. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted 5- to 10-membered heteroaryl group. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted 3- to 7-membered heterocyclic.

[0154] In certain embodiments, R.sup.1 and R.sup.2 are each independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, optionally substituted phenyl, or optionally substituted benzyl. In certain embodiments, R.sup.1 and R.sup.2 are both methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl or benzyl. In some embodiments, R.sup.1 and R.sup.2 are each butyl. In some embodiments, R.sup.1 and R.sup.2 are each isopropyl. In some embodiments, R.sup.1 and R.sup.2 are perfluoro. In some embodiments, R.sup.1 and R.sup.2 are CF.sub.2CF.sub.3. In some embodiments, R.sup.1 and R.sup.2 are each phenyl. In some embodiments, R.sup.1 and R.sup.2 are each benzyl.

[0155] In some embodiments, R.sup.1 and R.sup.2 are taken together with intervening atoms to form one or more optionally substituted rings. In certain embodiments, R.sup.1 and R.sup.2 are taken together to form a ring fragment selected from the group consisting of: C(R.sup.y).sub.2, C(R).sub.2C(R.sup.y).sub.2, C(R.sup.y).sub.2C(R.sup.y).sub.2C(R.sup.y).sub.2, C(R.sup.y).sub.2OC(R.sup.y).sub.2, and C(R).sub.2NR.sup.yC(R.sup.y).sub.2. In certain embodiments, R.sup.1 and R.sup.2 are taken together to form a ring fragment selected from the group consisting of: CH.sub.2, CH.sub.2CH.sub.2, CH.sub.2CH.sub.2CH.sub.2, CH.sub.2OCH.sub.2, and CH.sub.2NR.sup.yCH.sub.2. In some embodiments, R.sup.1 and R.sup.2 are taken together to form an unsaturated linker moiety optionally containing one or more additional heteroatoms. In some embodiments, the resulting nitrogen-containing ring is partially unsaturated. In certain embodiments, the resulting nitrogen-containing ring comprises a fused polycyclic heterocycle.

[0156] In specific embodiments, a protonated amine activating functional group is selected from the group consisting of:

##STR00043## ##STR00044##

[0157] In certain embodiments, an activating functional group is a guanidinium group:

##STR00045##

In some embodiments, each of R.sup.4, R.sup.5, R.sup.6, R.sup.7, and R.sup.8 is hydrogen. In some embodiments, each occurrence of R.sup.4, R.sup.5, R.sup.6, R.sup.7, and R.sup.8 is independently hydrogen or C.sub.1-20 aliphatic. In some embodiments, each occurrence of R.sup.4, R.sup.5, R.sup.6, R.sup.7, and R.sup.8 is independently hydrogen or C.sub.1-12 aliphatic. In some embodiments, each occurrence of R.sup.4, R.sup.5, R.sup.6, R.sup.7, and R.sup.8 is independently hydrogen or C.sub.1-20 heteroaliphatic. In some embodiments, each occurrence of R.sup.4, R.sup.5, R.sup.6, R.sup.7, and R.sup.8 is independently hydrogen or phenyl. In some embodiments, each occurrence of R.sup.4, R.sup.5, R.sup.6, R.sup.7, and R.sup.8 is independently hydrogen or 8- to 10-membered aryl. In some embodiments, each occurrence of R.sup.4, R.sup.5, R.sup.6, R.sup.7, and R.sup.8 is independently hydrogen or 5- to 10-membered heteroaryl. In some embodiments, each occurrence of R.sup.4, R.sup.5, R.sup.6, R.sup.7, and R.sup.8 is independently hydrogen or 3- to 7-membered heterocyclic. In some embodiments, one or more of R.sup.4, R.sup.5, R.sup.6, and R.sup.7 is optionally substituted C.sub.1-12 aliphatic. In certain embodiments, any of (R.sup.4 and R.sup.5), (R.sup.5 and R.sup.6), (R.sup.6 and R.sup.7), (R.sup.7 and R.sup.8), and (R.sup.4 and R.sup.7) can be taken together with intervening atoms to form one or more optionally substituted rings. In some embodiments, (R.sup.4 and R.sup.5) and (R.sup.6 and R.sup.7) are taken together to form rings.

[0158] It will be appreciated that when a guanidinium cation is depicted as

##STR00046##

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

##STR00047##

[0159] In specific embodiments, a guanidinium activating functional group is selected from the group consisting of:

##STR00048##

[0160] In some embodiments, an activating functional group is a sulfonium group or an arsonium group:

##STR00049##

where R.sup.8, R.sup.9, and R.sup.10 are as defined above.

[0161] In certain embodiments, each occurrence of R.sup.8, R.sup.9, and R.sup.10 is independently optionally substituted C.sub.1-20 aliphatic. In some embodiments, each occurrence of R.sup.8, R.sup.9, and R.sup.10 is independently hydrogen or optionally substituted C.sub.1-20 heteroaliphatic. In some embodiments, each occurrence of R.sup.9, R.sup.10, and R.sup.11 is independently hydrogen or optionally substituted phenyl. In some embodiments, each occurrence of R.sup.9, R.sup.10, and R.sup.11 is independently hydrogen or optionally substituted 8- to 10-membered aryl. In some embodiments, each occurrence of R.sup.8, R.sup.9, and R.sup.10 is independently hydrogen or optionally substituted 5- to 10-membered heteroaryl. In some embodiments, each occurrence of R.sup.9, R.sup.10, and R.sup.11 is independently hydrogen or optionally substituted 3- to 7-membered heterocyclic. In some embodiments, R.sup.8 and R.sup.9 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 C.sub.6-C.sub.10 aryl, and optionally substituted 5- to 10-membered heteroaryl.

[0162] In certain embodiments, R.sup.8, R.sup.9 and R.sup.10 are each methyl. In certain embodiments, R.sup.8, R.sup.9 and R.sup.10 are each phenyl.

[0163] In specific embodiments, an arsonium activating functional group is selected from the group consisting of:

##STR00050##

[0164] 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.

[0165] 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

##STR00051##

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.

[0166] 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.

[0167] In some embodiments, an activating functional group is

##STR00052##

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.

[0168] In some embodiments, R.sup.12 is hydrogen. In some embodiments, R.sup.12 is an optionally substituted C.sub.1-20 aliphatic group. In some embodiments, R.sup.12 is C.sub.1-20 heteroaliphatic. In some embodiments, R.sup.12 is optionally substituted phenyl, 8- to 10-membered aryl; 5- to 10-membered heteroaryl. In some embodiments, R.sup.12 is 3- to 7-membered heterocyclic. In some embodiments, R.sup.12 is an optionally substituted C.sub.1-12 aliphatic group. In some embodiments, R.sup.12 is neopentyl. In some embodiments, R.sup.12 is oxide or hydroxyl.

[0169] In some embodiments, when Z is

##STR00053##

ring A is other than an imidazole, an oxazole, or a thiazole.

[0170] In specific embodiments, a nitrogen-containing heterocycle activating functional group is selected from the group consisting of:

##STR00054## ##STR00055##

[0171] In some embodiments, an activating functional group is

##STR00056##

where R.sup.1, R.sup.2 and R.sup.5 are as defined above.

[0172] In certain embodiments, R.sup.1 and R.sup.2 are each hydrogen. In some embodiments, only one of R.sup.1 and R.sup.2 is hydrogen. In certain embodiments, R.sup.1 and R.sup.2 are each independently an optionally substituted radical selected from the group consisting of C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic, 5- to 14-membered heteroaryl, phenyl, 8- to 10-membered aryl and 3- to 7-membered heterocyclic. In certain embodiments, R.sup.1 and R.sup.2 are each independently an optionally substituted radical 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.

[0173] In certain embodiments, R.sup.1 and R.sup.2 are each independently an optionally substituted radical selected from the group consisting of C.sub.1-12 aliphatic and C.sub.1-12 heteroaliphatic. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted C.sub.1-20 aliphatic. In some embodiments, R.sup.1 and R.sup.2 are each independently optionally substituted C.sub.1-12 aliphatic. In some embodiments, R.sup.1 and R.sup.2 are each independently optionally substituted C.sub.1-6 aliphatic. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted C.sub.1-20 heteroaliphatic. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted C.sub.1-12 heteroaliphatic. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted 8- to 10-membered aryl. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted phenyl group. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted 5- to 10-membered heteroaryl group. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted 3- to 7-membered heterocyclic.

[0174] In certain embodiments, R.sup.1 and R.sup.2 are each independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, optionally substituted phenyl, or optionally substituted benzyl. In certain embodiments, R.sup.1 and R.sup.2 are both methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl or benzyl. In some embodiments, R.sup.1 and R.sup.2 are each butyl. In some embodiments, R.sup.1 and R.sup.2 are each isopropyl. In some embodiments, R.sup.1 and R.sup.2 are perfluoro. In some embodiments, R.sup.1 and R.sup.2 are CF.sub.2CF.sub.3. In some embodiments, R.sup.1 and R.sup.2 are each phenyl. In some embodiments, R.sup.1 and R.sup.2 are each benzyl.

[0175] In some embodiments, R.sup.1 and R.sup.2 are taken together with intervening atoms to form one or more optionally substituted rings. In certain embodiments, R.sup.1 and R.sup.2 are taken together to form a ring fragment selected from the group consisting of: C(R.sup.y).sub.2, C(R.sup.y).sub.2C(R.sup.y).sub.2, C(R.sup.y).sub.2C(R.sup.y).sub.2C(R.sup.y).sub.2, C(R.sup.y).sub.2OC(R.sup.y).sub.2, and C(R.sup.y).sub.2NR.sup.yC(R.sup.y).sub.2. In certain embodiments, R.sup.1 and R.sup.2 are taken together to form a ring fragment selected from the group consisting of: CH.sub.2, CH.sub.2CH.sub.2, CH.sub.2CH.sub.2CH.sub.2, CH.sub.2OCH.sub.2, and CH.sub.2NR.sup.yCH.sub.2. In some embodiments, R.sup.1 and R.sup.2 are taken together to form an unsaturated linker moiety optionally containing one or more additional heteroatoms. In some embodiments, the resulting nitrogen-containing ring is partially unsaturated. In certain embodiments, the resulting nitrogen-containing ring comprises a fused polycyclic heterocycle.

[0176] In certain embodiments, R.sup.5 is H. In certain embodiments, R.sup.5 is optionally substituted C.sub.1-20 aliphatic, and in some embodiments R.sup.5 is optionally substituted 6- to 14-membered aryl. In certain embodiments, R.sup.5 is optionally substituted C.sub.1-12 aliphatic and in some embodiments, optionally substituted C.sub.1-6 aliphatic. In certain embodiments, R.sup.5 is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl or benzyl. In some embodiments, R.sup.5 is perfluoro. In some embodiments, R.sup.5 is-CF.sub.2CF.sub.3. In certain embodiments, R.sup.5 is optionally substituted phenyl.

[0177] In some embodiments, one or more R.sup.1 or R.sup.2 groups are taken together with R.sup.5 and intervening atoms to form an optionally substituted ring. In certain embodiments, R.sup.1 and R.sup.5 are taken together to form an optionally substituted 5- or 6-membered ring. In some embodiments, R.sup.2 and R.sup.5 are taken together to form an optionally substituted 5- or 6-membered ring optionally containing one or more additional heteroatoms. In some embodiments, R.sup.1, R.sup.2 and R.sup.5 are taken together to form an optionally substituted fused ring system. In some embodiments such rings formed by combinations of any of R.sup.1, R.sup.2 and R.sup.5 are partially unsaturated or aromatic.

[0178] In some embodiments, an activating functional group is

##STR00057##

where R.sup.1 and R.sup.2 are as defined above.

[0179] In certain embodiments, R.sup.1 and R.sup.2 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.1 and R.sup.2 are each independently an optionally substituted 4-7-membered heterocyclic. In some embodiments, R.sup.1 and R.sup.2 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.1 and R.sup.2 are each independently selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, or benzyl. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently perfluoro. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently CF.sub.2CF.sub.3.

[0180] In some embodiments, an activating functional group is

##STR00058##

where R.sup.1, R.sup.2, R.sup.3, and R.sup.5 are as defined above.

[0181] In certain embodiments, R.sup.1, R.sup.2, and R.sup.3 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 certain embodiments, R.sup.1, R.sup.2, and R.sup.3 are each independently an optionally substituted 4-7-membered heterocyclic. In some embodiments, R.sup.1 and R.sup.2 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 certain embodiments, R.sup.1, R.sup.2, and R.sup.3 are each independently an optionally substituted C.sub.1-6 aliphatic. In certain embodiments, R.sup.1, R.sup.2, and R.sup.3 are each independently selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, or benzyl. In certain embodiments, R.sup.1, R.sup.2, and R.sup.3 are each independently perfluoro. In some embodiments, R.sup.1, R.sup.2, and R.sup.3 are each independently CF.sub.2CF.sub.3.

[0182] In certain embodiments, R.sup.5 is hydrogen. In certain embodiments R.sup.5 is an optionally substituted group selected from the group consisting of C.sub.1-12 aliphatic and C.sub.1-12 heteroaliphatic. In some embodiments, R.sup.5 is an optionally substituted C.sub.1-12 aliphatic. In some embodiments, R.sup.5 is optionally substituted C.sub.1-6 aliphatic.

[0183] In some embodiments, an activating functional group is

##STR00059##

In certain embodiments, R.sup.1 and R.sup.2 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.1 and R.sup.2 are each independently an optionally substituted 4-7-membered heterocyclic. In some embodiments, R.sup.1 and R.sup.2 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.1 and R.sup.2 are each independently selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, or benzyl. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently perfluoro. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently CF.sub.2CF.sub.3.

[0184] In certain embodiments, R.sup.5 and R.sup.6 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.5 and R.sup.6 are each independently an optionally substituted C.sub.1-20 aliphatic. In some embodiments, R.sup.5 and R.sup.6 are each independently an optionally substituted C.sub.1-20 heteroaliphatic having. In some embodiments, R.sup.5 and R.sup.6 are each independently an optionally substituted phenyl or 8-10-membered aryl. In some embodiments, R.sup.5 and R.sup.6 are each independently an optionally substituted 5- to 10-membered heteroaryl. In some embodiments, R.sup.3 and R.sup.4 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.5 and R.sup.6 are each independently an optionally substituted C.sub.1-6 aliphatic. In some embodiments, each occurrence of R.sup.5 and R.sup.6 is independently methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, or benzyl. In some embodiments, each occurrence of R.sup.5 and R.sup.6 is independently perfluoro. In some embodiments, each occurrence of R.sup.5 and R.sup.6 is independently CF.sub.2CF.sub.3.

[0185] In some embodiments, an activating functional group is

##STR00060##

where R.sup.1 and R.sup.2 are as defined above.

[0186] In certain embodiments, R.sup.1 and R.sup.2 are each hydrogen. In some embodiments, only one of R.sup.1 and R.sup.2 is hydrogen. In certain embodiments, R.sup.1 and R.sup.2 are each independently 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.

[0187] In certain embodiments, R.sup.1 and R.sup.2 are each independently an optionally substituted radical selected from the group consisting of C.sub.1-12 aliphatic and C.sub.1-12 heteroaliphatic. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted C.sub.1-20 aliphatic. In some embodiments, R.sup.1 and R.sup.2 are each independently optionally substituted C.sub.1-12 aliphatic. In some embodiments, R.sup.1 and R.sup.2 are each independently optionally substituted C.sub.1-6 aliphatic. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted C.sub.1-20 heteroaliphatic. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted C.sub.1-12 heteroaliphatic. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted phenyl or 8- to 10-membered aryl. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted phenyl group. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted 5- to 10-membered heteroaryl group. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted 3- to 7-membered heterocyclic.

[0188] In certain embodiments, R.sup.1 and R.sup.2 are each independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, optionally substituted phenyl, or optionally substituted benzyl. In certain embodiments, R.sup.1 and R.sup.2 are both methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl or benzyl. In some embodiments, R.sup.1 and R.sup.2 are each butyl. In some embodiments, R.sup.1 and R.sup.2 are each isopropyl. In some embodiments, R.sup.1 and R.sup.2 are perfluoro. In some embodiments, R.sup.1 and R.sup.2 are CF.sub.2CF.sub.3. In some embodiments, R.sup.1 and R.sup.2 are each phenyl. In some embodiments, R.sup.1 and R.sup.2 are each benzyl.

[0189] In some embodiments, R.sup.1 and R.sup.2 are taken together with intervening atoms to form one or more optionally substituted rings. In certain embodiments, R.sup.1 and R.sup.2 are taken together to form a ring fragment selected from the group consisting of: C(R.sup.y).sub.2, C(R.sup.y).sub.2C(R.sup.y).sub.2, C(R.sup.y).sub.2C(R.sup.y).sub.2C(R.sup.y).sub.2, C(R.sup.y).sub.2OC(R.sup.y).sub.2, and C(R.sup.y).sub.2NR.sup.yC(R.sup.y).sub.2. In certain embodiments, R.sup.1 and R.sup.2 are taken together to form a ring fragment selected from the group consisting of: CH.sub.2, CH.sub.2CH.sub.2, CH.sub.2CH.sub.2CH.sub.2, CH.sub.2OCH.sub.2, and CH.sub.2NR.sup.yCH.sub.2. In some embodiments, R.sup.1 and R.sup.2 are taken together to form an unsaturated linker moiety optionally containing one or more additional heteroatoms. In some embodiments, the resulting nitrogen-containing ring is partially unsaturated. In certain embodiments, the resulting nitrogen-containing ring comprises a fused polycyclic heterocycle.

[0190] In some embodiments, an activating functional group is

##STR00061##

In certain embodiments, R.sup.1, R.sup.2, and R.sup.3 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 certain embodiments, R.sup.1, R.sup.2, and R.sup.3 are each independently an optionally substituted 4-7-membered heterocyclic. In some embodiments, R.sup.1 and R.sup.2 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 certain embodiments, R.sup.1, R.sup.2, and R.sup.3 are each independently an optionally substituted C.sub.1-6 aliphatic. In certain embodiments, R.sup.1, R.sup.2, and R.sup.3 are each independently selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, or benzyl. In certain embodiments, R.sup.1, R.sup.2, and R.sup.3 are each independently perfluoro. In some embodiments, R.sup.1, R.sup.2, and R.sup.3 are each independently CF.sub.2CF.sub.3.

[0191] In some embodiments, an activating functional group is

##STR00062##

where R.sup.1 and R.sup.2 are as defined above.

[0192] In certain embodiments, R.sup.1 and R.sup.2 are each hydrogen. In some embodiments, only one of R.sup.1 and R.sup.2 is hydrogen. In certain embodiments, R.sup.1 and R.sup.2 are each independently 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.

[0193] In certain embodiments, R.sup.1 and R.sup.2 are each independently an optionally substituted radical selected from the group consisting of C.sub.1-12 aliphatic and C.sub.1-12 heteroaliphatic. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted C.sub.1-20 aliphatic. In some embodiments, R.sup.1 and R.sup.2 are each independently optionally substituted C.sub.1-12 aliphatic. In some embodiments, R.sup.1 and R.sup.2 are each independently optionally substituted C.sub.1-6 aliphatic. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted C.sub.1-20 heteroaliphatic. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted C.sub.1-12 heteroaliphatic. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted 8- to 10-membered aryl. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted phenyl group. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted 5- to 10-membered heteroaryl group. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently an optionally substituted 3- to 7-membered heterocyclic.

[0194] In certain embodiments, R.sup.1 and R.sup.2 are each independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, optionally substituted phenyl, or optionally substituted benzyl. In certain embodiments, R.sup.1 and R.sup.2 are both methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl or benzyl. In some embodiments, R.sup.1 and R.sup.2 are each butyl. In some embodiments, R.sup.1 and R.sup.2 are each isopropyl. In some embodiments, R.sup.1 and R.sup.2 are perfluoro. In some embodiments, R.sup.1 and R.sup.2 are CF.sub.2CF.sub.3. In some embodiments, R.sup.1 and R.sup.2 are each phenyl. In some embodiments, R.sup.1 and R.sup.2 are each benzyl.

[0195] In some embodiments, R.sup.1 and R.sup.2 are taken together with intervening atoms to form one or more optionally substituted rings. In certain embodiments, R.sup.1 and R.sup.2 are taken together to form a ring fragment selected from the group consisting of: C(R.sup.y).sub.2, C(R).sub.2C(R.sup.y).sub.2, C(R.sup.y).sub.2C(R.sup.y).sub.2C(R.sup.y).sub.2, C(R).sub.2OC(R.sup.y).sub.2, and C(R.sup.y).sub.2NR.sup.yC(R.sup.y).sub.2. In certain embodiments, R.sup.1 and R.sup.2 are taken together to form a ring fragment selected from the group consisting of: CH.sub.2, CH.sub.2CH.sub.2, CH.sub.2CH.sub.2CH.sub.2, CH.sub.2OCH.sub.2, and CH.sub.2NR.sup.yCH.sub.2. In some embodiments, R.sup.1 and R.sup.2 are taken together to form an unsaturated linker moiety optionally containing one or more additional heteroatoms. In some embodiments, the resulting nitrogen-containing ring is partially unsaturated. In certain embodiments, the resulting nitrogen-containing ring comprises a fused polycyclic heterocycle.

[0196] In some embodiments, an activating functional group is

##STR00063##

In certain embodiments, R.sup.1 and R.sup.2 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.1 and R.sup.2 are each independently an optionally substituted 4-7-membered heterocyclic. In some embodiments, R.sup.1 and R.sup.2 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.1 and R.sup.2 are each independently selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, or benzyl. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently perfluoro. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently CF.sub.2CF.sub.3.

[0197] In some embodiments, an activating functional group is

##STR00064##

In certain embodiments, R.sup.1, R.sup.2, and R.sup.3 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 certain embodiments, R.sup.1, R.sup.2, and R.sup.3 are each independently an optionally substituted 4-7-membered heterocyclic. In some embodiments, R.sup.1 and R.sup.2 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 certain embodiments, R.sup.1, R.sup.2, and R.sup.3 are each independently an optionally substituted C.sub.1-6 aliphatic. In certain embodiments, R.sup.1, R.sup.2, and R.sup.3 are each independently selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, or benzyl. In certain embodiments, R.sup.1, R.sup.2, and R.sup.3 are each independently perfluoro. In some embodiments, R.sup.1, R.sup.2, and R.sup.3 are each independently CF.sub.2CF.sub.3.

[0198] In some embodiments, an activating functional group is

##STR00065##

where R.sup.1 and R.sup.2 are as defined above.

[0199] In certain embodiments, R.sup.1 and R.sup.2 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.1 and R.sup.2 are each independently an optionally substituted 4-7-membered heterocyclic. In some embodiments, R.sup.1 and R.sup.2 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.1 and R.sup.2 are each independently selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, or benzyl. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently perfluoro. In some embodiments, each occurrence of R.sup.1 and R.sup.2 is independently CF.sub.2CF.sub.3.

[0200] In certain embodiments, X is any anion. In certain embodiments, X is a nucleophile. In some embodiments, X is a nucleophile capable of ring opening an epoxide. In certain embodiments, X is absent. In certain embodiments, X is a nucleophilic ligand. Exemplary nucleophilic ligands include, but are not limited to, OR.sup.x, SR.sup.x, O(CO)R.sup.x, O(CO)OR.sup.x, O(CO)N(R.sup.x).sub.2, N(R.sup.x)(CO)R.sup.x, NC, CN, halo (e.g., Br, I, Cl), N.sub.3, O(SO.sub.2)R.sup.x and OPR.sup.x.sub.3, wherein each R.sup.x is, independently, selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl and optionally substituted heteroaryl.

[0201] In certain embodiments, X is O(CO)R.sup.x, wherein R.sup.x is selected from optionally substituted aliphatic, fluorinated aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, fluorinated aryl, and optionally substituted heteroaryl.

[0202] For example, in certain embodiments, X is O(CO)R.sup.x, wherein R.sup.x is optionally substituted aliphatic. In certain embodiments, X is O(CO)R.sup.x, wherein R.sup.x is optionally substituted alkyl and fluoroalkyl. In certain embodiments, X is O(CO)CH.sub.3 or O(CO)CF.sub.3.

[0203] Furthermore, in certain embodiments, X is O(CO)R.sup.x, wherein R.sup.x is optionally substituted aryl, fluoroaryl, or heteroaryl. In certain embodiments, X is O(CO)R.sup.x, wherein R.sup.x is optionally substituted aryl. In certain embodiments, X is O(CO)R.sup.x, wherein R.sup.x is optionally substituted phenyl. In certain embodiments, X is O(CO)C.sub.6H.sub.5 or O(CO)C.sub.6F.sub.5.

[0204] In certain embodiments, X is OR.sup.x, wherein R.sup.x is selected from optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, and optionally substituted heteroaryl.

[0205] For example, in certain embodiments, X is OR.sup.x, wherein R.sup.x is optionally substituted aryl. In certain embodiments, X is OR.sup.x, wherein R.sup.x is optionally substituted phenyl. In certain embodiments, X is OC.sub.6H.sub.5 or OC.sub.6H.sub.2(2,4-NO.sub.2).

[0206] In certain embodiments, X is halo. In certain embodiments, X is Br. In certain embodiments, X is Cl. In certain embodiments, X is I.

[0207] In certain embodiments, X is O(SO.sub.2)R.sup.x. In certain embodiments X is OTs. In certain embodiments X is OSO.sub.2Me. In certain embodiments X is OSO.sub.2CF.sub.3. In some embodiments, X is a 2,4-dinitrophenolate anion.

I.c. Phosphorous-Containing Activating Groups

[0208] In some embodiments, activating functional groups Z are phosphorous containing groups.

[0209] In certain embodiments, a phosphorous-containing functional group is chosen from the group consisting of: phosphines (PR.sup.y.sub.2); Phosphine oxides P(O)R.sup.y.sub.2; phosphinites P(OR.sup.7)R.sup.y.sub.2; phosphonites P(OR.sup.7).sub.2R.sup.y; phosphites P(OR.sup.7).sub.3; phosphinates OP(OR.sup.7)R.sup.y.sub.2; phosphonates; OP(OR.sup.7).sub.2R.sup.y; phosphates OP(OR.sup.7).sub.3; phosponium salts ([PR.sup.y.sub.3].sup.+) where a phosphorous-containing functional group may be linked to a metal complex through any available position (e.g. direct linkage via the phosphorous atom, or in some cases via an oxygen atom).

[0210] In certain embodiments, a phosphorous-containing functional group is chosen from the group consisting of:

##STR00066##

or a combination of two or more of these [0211] wherein R.sup.1 and R.sup.2, are as defined above; and [0212] each R.sup.7, is independently 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; and where two R.sup.7 groups can be taken together with intervening atoms to form an optionally substituted ring optionally containing one or more heteroatoms, and an R.sup.7 group can be taken with an R.sup.1 or R.sup.2 group to an optionally substituted ring;

[0213] In some embodiments, phosphorous containing functional groups include those disclosed in The Chemistry of Organophosphorus Compounds. Volume 4. Ter-and Quinquevalent Phosphorus Acids and their Derivatives. The Chemistry of Functional Group Series Edited by Frank R. Hartley (Cranfield University, Cranfield, U.K.). Wiley: New York. 1996. ISBN 0-471-95706-2, the entirety of which is hereby incorporated herein by reference.

*(X).sub.b[(R.sup.6R.sup.7R.sup.8P).sup.+].sub.nQ.sup.n-, wherein: [0214] X is O, N, or NR.sup.z, [0215] b is 1 or 0, [0216] each of R.sup.6, R.sup.7 and R.sup.8 are independently present or absent and, if present, are independently selected from the group consisting of optionally substituted C.sub.1-C.sub.20 aliphatic, optionally substituted phenyl, optionally substituted C.sub.8-C.sub.14 aryl, optionally substituted 3- to 14-membered heterocyclic, optionally substituted 5- to 14-membered heteroaryl, halogen, O, OR.sup.z, NR.sup.z, and N(R.sup.z).sub.2 where R.sup.z is hydrogen, or an optionally substituted C.sub.1-C.sub.20 aliphatic, optionally substituted phenyl, optionally substituted 8- to 14-membered aryl, optionally substituted 3- to 14-membered heterocyclic, or optionally substituted 5- to 14-membered heteroaryl, [0217] Q is any anion, and [0218] n is an integer between 1 and 4.

[0219] In some embodiments, an activating functional group is a phosphonate group:

##STR00067##

wherein R.sup.1, R.sup.2, and R.sup.7 is as defined above.

[0220] In specific embodiments, a phosphonate activating functional group is selected from the group consisting of:

##STR00068##

[0221] In some embodiments, an activating functional group is a phosphonic diamide group:

##STR00069##

wherein R.sup.1, R.sup.2, and R.sup.7, are as defined above. In certain embodiments, each R.sup.1 and R.sup.2 group in a phosphonic diamide is methyl.

[0222] In some embodiments, an activating functional group is a phosphine group:

##STR00070##

wherein R.sup.1, and R.sup.2 are as defined above.

[0223] In specific embodiments, a phosphine activating functional group is selected from the group consisting of:

##STR00071##

II. Linker Moieties

[0224] As described above, each activating moiety (Z).sub.m comprises a linker coupled to at least one activating functional group Z as described above, with m denoting the number of activating functional groups present on a single linker moiety.

[0225] 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.

[0226] 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.

[0227] 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, 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, and NR.sup.yC(O)OR.sup.y, 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.

[0228] 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 gem-dimethyl substituted carbon atoms.

[0229] 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.

[0230] 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 sprirocyclic rings, gem dimethyl groups, gem diethyl groups and gem diphenyl groups. In certain embodiments such structural constraints are selected from the group consisting of heteratom-containing functional groups such as sulfoxides, amides, and oximes.

[0231] In certain embodiments, linker moieties are selected from the group consisting of:

##STR00072## ##STR00073##

[0232] where * represents the site of attachment to a ligand, and each # represents a site of attachment of an activating functional group.

[0233] 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.

[0234] In some embodiments, t is 1. In some embodiments, t is 2. In some embodiments, t is 3. In some embodiments, t is 4.

III. Metal Complexes

[0235] As noted above, the present invention encompasses metal complexes that include a metal atom coordinated to a multidentate ligand and at least one activating moiety tethered to a multidentate ligand. In certain embodiments, provided metal complexes have the structure:

##STR00074##

where

##STR00075##

represents a metal atom coordinated to a multidentate ligand.
III.a. Metal Atoms

[0236] 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.

[0237] 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+.

III.b. Ligands

[0238] In some embodiments, a metal complex

##STR00076##

comprises a metal atom coordinated to a single tetradentate ligand and in some embodiments, the metal complex comprises a chelate containing a plurality of individual ligands. In certain embodiments, a metal complex contains two bidentate ligands. In some embodiments, a metal complex contains a tridentate ligand.

[0239] In various embodiments, tetradentate ligands suitable for metal complexes of the present invention may include, but are not limited to: salen derivatives 1, derivatives of salan ligands 2, bis-2-hydroxybenzamido derivatives 3, derivatives of the Trost ligand 4, porphyrin derivatives 5, derivatives of tetrabenzoporphyrin ligands 6, derivatives of corrole ligands 7, phthalocyaninate derivatives 8, and dibenzotetramethyltetraaza[14]annulene (tmtaa) derivatives 9 or 9.

##STR00077## ##STR00078##

[0240] In some embodiments, a metal multidentate ligand coordinated with a metal complex may comprise a plurality of discrete ligands. In some embodiments, metal complexes include two bidentate ligands. In certain embodiments, such bidentate ligands may have the structure

##STR00079##

where R.sup.d and R.sup.1 are as defined above. Metal complexes having two such ligands may adopt one of several geometries, and the present disclosure encompasses such variations.

[0241] In certain embodiments, metal complexes including two bidentate ligands may have structures selected from the group consisting of:

##STR00080##

where each

##STR00081##

represents a ligand:

##STR00082##

[0242] In certain embodiments, a tetradentate ligand is a salen ligand. In certain embodiments, a metal complex is a metallosalenate. In certain embodiments, a metal complex is a cobalt salen complex. In certain embodiments, a metal complex is a chromium salen complex. In some embodiments, a metal complex is an aluminum salen complex.

[0243] In certain embodiments, at least one activating moiety is tethered to a carbon atom of a phenyl ring of the salicylaldehyde-derived portions of a salen ligand. In certain embodiments, at least one activating moiety is tethered to a carbon atom of a porphyrin ligand. In certain embodiments, at least one activating moiety is tethered to a pyrrole-carbon atom of a porphyrin ligand. In certain embodiments, at least one activating moiety is tethered to a carbon atom forming the bridge between the pyrrole rings of a porphyrin ligand.

[0244] 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:

##STR00083##

wherein: [0245] M is a metal atom; [0246] X is a nucleophile capable of ring opening an epoxide; [0247] k is an integer from 0-2 inclusive; [0248] 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, 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; [0249] 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;

##STR00084##

represents is an optionally substituted moiety linking the two nitrogen atoms of the diamine portion of the salen ligand, where

##STR00085##

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; [0250] (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 m is an integer from 1 to 4 indicating the number of individual activating functional groups present in each activating moiety.

[0251] In certain embodiments, both salicylaldehyde-derived portions of a salen ligand bear one or more activating moieties:

##STR00086##

wherein M, X, k, R,

##STR00087##

and (Z).sub.m are as defined above.

[0252] In some embodiments, provided metal complexes comprise a

##STR00088##

moiety that has the structure:

##STR00089##

wherein: [0253] M is a metal atom, [0254] R.sup.1a, R.sup.1a, R.sup.2a, R.sup.2a, R.sup.3a, and R.sup.3a are 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; each R is independently hydrogen, an optionally substituted radical selected the group consisting of acyl; carbamoyl; arylalkyl; phenyl, 8- to 10-membered aryl; C.sub.1-12 aliphatic; C.sub.1-12 heteroaliphatic; 5- to 10-membered heteroaryl; 4- to 7-membered heterocyclyl; an oxygen protecting group; and a nitrogen protecting group; or: [0255] two R on the same nitrogen atom are taken with the nitrogen to form a 3- to 7-membered heterocyclic ring; [0256] wherein any of [R.sup.2a and R.sup.3a], [R.sup.2a and R.sup.3a], [R.sup.1a and R.sup.2a], and [R.sup.1a and R.sup.2a] may optionally be taken together with the carbon atoms to which they are attached to form one or more rings which may in turn be substituted with one or more R.sup.20a groups; and [0257] R.sup.4a is selected from the group consisting of:

##STR00090##

where [0258] R.sup.c at each occurrence is independently a Z 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; [0259] where: [0260] two or more Re groups may be taken together with the carbon atoms to which they are attached and any intervening atoms to form one or more rings; [0261] when two Re groups are attached to the same carbon atom, they may be taken together along with the carbon atom to which they are attached to form a moiety selected from the group consisting of: a 3- to 8-membered spirocyclic ring, a carbonyl, an oxime, a hydrazone, an imine; [0262] X is a nucleophile capable of ring opening an epoxide; [0263] Y is a divalent linker selected from the group consisting of: NR, N(R)C(O), C(O)NR, O, C(O), OC(O), C(O)O, S, SO, SO.sub.2, C(S), C(NR), or NN; a polyether; a C.sub.3 to C.sub.8 substituted or unsubstituted carbocycle; and a C.sub.1 to C.sub.8 substituted or unsubstituted heterocycle; [0264] m is 0 or an integer from 1 to 4, inclusive; [0265] q is 0 or an integer from 1 to 4, inclusive; and [0266] x is 0, 1, or 2.

[0267] In some embodiments, at least one of [R.sup.2a and R.sup.3a] and [R.sup.2a and R.sup.3a] are taken together to form a ring. In some embodiments, both [R.sup.2a and R.sup.3a] and [R.sup.2a and R.sup.3a] are taken together to form rings. In some embodiments, the rings formed by [R.sup.2a and R.sup.3a] and [R.sup.2a and R.sup.3a] are substituted phenyl rings.

[0268] In certain embodiments, one or more of R.sup.1a, R.sup.1a, R.sup.2a, R.sup.2a, R.sup.3a, and R.sup.3a are independently a Z group.

[0269] In certain embodiments of provided metal complexes, a

##STR00091##

moiety has a structure selected from the group consisting of:

##STR00092##

wherein: [0270] M is a metal atom; [0271] 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 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; [0272] 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; [0273] n is 0 or an integer from 1 to 8, inclusive; and [0274] p is 0 or an integer from 1 to 4, inclusive.

[0275] In some embodiments, M is Co.

[0276] 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.5, R.sup.5a, R.sup.7a and R.sup.7a is a Z group. In some embodiments, R.sup.5a and R.sup.5a are a Z group.

[0277] In certain embodiments of provided metal complexes, a

##STR00093##

moiety has a structure selected from the group consisting of:

##STR00094##

[0278] In certain embodiments of complexes having formulae described above, at least one of the phenyl rings comprising a salicylaldehyde-derived portion of a catalyst is independently selected from the group consisting of:

##STR00095## ##STR00096## ##STR00097## ##STR00098## ##STR00099##

[0279] where (Z).sub.m represents one or more independently-defined activating moieties which may be bonded to any one or more unsubstituted positions of a salicylaldehyde-derived phenyl ring.

[0280] In certain embodiments, there is an activating moiety tethered to the position ortho to a metal-bound oxygen substituent of one or both of the salicylaldehyde-derived phenyl rings of a salen ligand as in formulae IIIa and IIIb:

##STR00100##

wherein: [0281] M, X, k, R,

##STR00101##

and (Z).sub.m are as defined above, and [0282] R.sup.4a, R.sup.4a, R.sup.5a, R.sup.5a, R.sup.6a, and R.sup.6a are each independently a Z 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; [0283] wherein any two adjacent R.sup.4a, R.sup.4a, R.sup.5a, R.sup.5a, R.sup.6a, and R.sup.6a groups can be taken together with intervening atoms to form one or more optionally substituted rings.

[0284] In certain embodiments of compounds having formulae IIIa or IIIb, R.sup.4a, R.sup.4a, R.sup.6a, and R.sup.6a are each hydrogen, and R.sup.5a, R.sup.5a are, independently, optionally substituted C.sub.1-C.sub.20 aliphatic.

[0285] In certain embodiments of complexes IIIa and IIIb, at least one of the phenyl rings comprising a salicylaldehyde-derived portion of a catalyst is independently selected from the group consisting of:

##STR00102## ##STR00103##

[0286] In certain embodiments, there is an activating moiety tethered to the position para to the phenolic oxygen of one or both of a salicylaldehyde-derived phenyl rings of the salen ligand as in structures IVa and IVb:

##STR00104##

[0287] where M, X, k, R, R.sup.4a, R.sup.4a, R.sup.6a, R.sup.6a, R.sup.7a, R.sup.7a,

##STR00105##

and (Z).sub.m are as defined above.

[0288] In certain embodiments of compounds having formulae IVa or IVb, R.sup.4a, R.sup.4a, R.sup.6a, and R.sup.6a are hydrogen, and each R.sup.7a, R.sup.7a is, independently, optionally substituted C.sub.1-C.sub.20 aliphatic.

[0289] In certain embodiments of catalysts IVa and IVb, at least one of the phenyl rings comprising a salicylaldehyde-derived portion of a catalyst is independently selected from the group consisting of:

##STR00106## ##STR00107##

[0290] In some embodiments, there is an activating moiety tethered to the position para to the imine substituent of one or both of the salicylaldehyde-derived phenyl rings of a salen ligand as in formulae Va or Vb:

##STR00108##

[0291] where M, X, k, R, R.sup.4a, R.sup.4a, R.sup.5a, R.sup.5a, R.sup.7a, R.sup.7a,

##STR00109##

and (Z).sub.m are as defined above.

[0292] In certain embodiments of compounds having formulae Va or Vb, each R.sup.4 and R.sup.4a is hydrogen, and each R.sup.5a, R.sup.5a, R.sup.7a, R.sup.7a is, independently, hydrogen or optionally substituted C.sub.1-C.sub.20 aliphatic.

[0293] In certain embodiments of catalysts Va and Vb, at least one of the phenyl rings comprising a salicylaldehyde-derived portion of a catalyst is independently selected from the group consisting of:

##STR00110## ##STR00111## ##STR00112##

[0294] 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 formulae VIa and VIb:

##STR00113##

where X, k, M, R, R.sup.5a, R.sup.5a, R.sup.6a, R.sup.6a, R.sup.7a, R.sup.7a,

##STR00114##

and (Z) are as defined above.

[0295] In certain embodiments of compounds having formulae VIa or VIb, each R.sup.6a and R.sup.6a is hydrogen, and each R.sup.5a, R.sup.5a, R.sup.7a, and R.sup.7 is, independently, hydrogen or optionally substituted C.sub.1-C.sub.20 aliphatic.

[0296] In certain embodiments of catalysts VIa and VIb, at least one of the phenyl rings comprising a salicylaldehyde-derived portion of a catalyst is independently selected from the group consisting of:

##STR00115## ##STR00116## ##STR00117## ##STR00118##

[0297] In some embodiments, there are activating moieties tethered to the positions ortho and para to the phenolic oxygen of one or both of the salicylaldehyde-derived phenyl rings of a salen ligand as in formulae VIIa and VIIb:

##STR00119##

where M, X, k, R, R.sup.4a, R.sup.4a, R.sup.6a, R.sup.6a,

##STR00120##

and (Z).sub.m are as defined above.

[0298] In certain embodiments of compounds having formulae VIa or VIb, each R.sup.6a, R.sup.6a, R.sup.4a, and R.sup.4a is, independently, hydrogen or optionally substituted C.sub.1-C.sub.20 aliphatic.

[0299] In certain embodiments of compounds having formulae VIIa or VIIb, each R.sup.6a, R.sup.6a, R.sup.4a, and R.sup.4a is hydrogen.

[0300] In some embodiments, there are activating moieties tethered to the positions ortho and para to the imine substituent of one or both of the salicylaldehyde-derived phenyl rings of a salen ligand as in formulae VIIIa and VIIIb:

##STR00121##

where X, k, M, R, R.sup.5a, R.sup.5a, R.sup.7a, R.sup.7a,

##STR00122##

and (Z).sub.m are as defined above.

[0301] In certain embodiments of compounds having formulae VIIIa or VIIIb, each R.sup.5a, R.sup.5a, R.sup.7a, and R.sup.7a is, independently, optionally, hydrogen or substituted C.sub.1-C.sub.20 aliphatic.

[0302] In certain embodiments of the present invention, catalysts of structures VIIIa or VIIIb above, at least one of the phenyl rings comprising the salicylaldehyde-derived portion of a catalyst is independently selected from the group consisting of:

##STR00123## ##STR00124## ##STR00125## ##STR00126##

[0303] In some embodiments, there is an activating moiety tethered to the imine carbon of a salen ligand as in formulae IXa and IXb:

##STR00127##

where M, X, k, M, R.sup.4a, R.sup.4a, R.sup.5a, R.sup.5a, R.sup.6a, R.sup.6a, R.sup.7a, R.sup.7a,

##STR00128##

and (Z).sub.m are as defined above with the proviso that the atom of the activating moiety attached to the salen ligand is a carbon atom.

[0304] In certain embodiments of compounds having formulae IXa or IXb, each R.sup.4a, R.sup.4a, R.sup.6a, and R.sup.6a is hydrogen, and each R.sup.5a, R.sup.5a, R.sup.7a, and R.sup.7a is, independently, hydrogen or optionally substituted C.sub.1-C.sub.20 aliphatic.

[0305] In certain embodiments of the present invention, catalysts of structures VIIIa or IXa or IXb above, at least one of the phenyl rings comprising the salicylaldehyde-derived portion of a catalyst is independently selected from the group consisting of:

##STR00129## ##STR00130## ##STR00131## ##STR00132##

[0306] As shown above, the two phenyl rings derived from salicylaldehyde in the core salen structures need not be the same. Though not explicitly shown in formulae Ia through IXb above, it is to be understood that a catalyst may have an activating moiety attached to different positions on each of the two rings, and such compounds are specifically encompassed within the scope of the present invention. Furthermore, activating moieties can be present on multiple parts of the ligand, for instance activating moieties can be present on the diamine bridge and on one or both phenyl rings in the same catalyst.

[0307] In certain embodiments, the salen ligand cores of catalysts Ia through IXb above are selected from the group shown below wherein any available position may be independently substituted with one or more R-groups or one or more activating moieties as described above.

##STR00133##

[0308] where M, X, and k, are as defined above.

[0309] In some embodiments, at least one activating moiety is tethered to the diamine-derived portion of the salen ligand, as shown in formula X:

##STR00134##

where M, X, k, R,

##STR00135##

and (Z).sub.m are as defined above.

[0310] In certain embodiments, salen ligands of formula X are selected from an optionally substituted moiety consisting of:

##STR00136##

where M, X, k, R, and (Z).sub.m are as defined above.

[0311] In certain embodiments, the diamine bridge of catalysts of formula Xa an optionally substituted moiety selected from the group consisting of:

##STR00137## ##STR00138##

where M and (Z).sub.m is as defined above.

[0312] In certain embodiments, metallosalenate complexes of the present invention include, but are not limited to those in Table 1 below:

TABLE-US-00003 TABLE 1 [00139] [00140] [00141] [00142] [00143] [00144] [00145] [00146] [00147] [00148] [00149] [00150] [00151] [00152] [00153] [00154] [00155] [00156] [00157] [00158] [00159] [00160] [00161] [00162] [00163] [00164] [00165] [00166] [00167] [00168] [00169] [00170] [00171] [00172] [00173] [00174] [00175] [00176] [00177] [00178] [00179] [00180] [00181] [00182] [00183] [00184] [00185] [00186] [00187] [00188] [00189] [00190] [00191] [00192] [00193] [00194] [00195] [00196] [00197] [00198] [00199] [00200] [00201] [00202] [00203] [00204] [00205] [00206] [00207] [00208] [00209] [00210] [00211] [00212] [00213] [00214] [00215] [00216] [00217] [00218] [00219] [00220] [00221] [00222] [00223] [00224] [00225] [00226] [00227] [00228] [00229] [00230] [00231] [00232] [00233] [00234] [00235] [00236] [00237] [00238] [00239] [00240]

[0313] In certain embodiments, for complexes of Table 1, M is CoX, where X is as defined above. 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 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.

[0314] In some embodiments, for complexes of Table 1, M is CrX, where X is as defined above.

[0315] In certain embodiments, a tetradentate ligand is a porphyrin ligand. In some embodiments, a metal complex is a cobalt porphyrin complex. In certain embodiments, a metal complex is a chromium porphyrin complex. In some embodiments, a metal complex is an aluminum porphyrin complex.

[0316] Examples of porphyrin containing metal complexes of the present invention include, but are not limited to:

##STR00241## ##STR00242##

[0317] wherein each of M, X, k, R, and (Z).sub.m is as defined above.

[0318] In certain embodiments, a multidentate ligand is an optionally substituted tetrabenzoporphyrin. Suitable examples include, but are not limited to:

##STR00243## ##STR00244##

wherein M, R, and (Z).sub.n are as previously defined.

[0319] In certain embodiments of porphyrin and phthalocyanine-based complexes described herein, M is aluminum. In certain embodiments of porphyrin and phthalocyanine-based complexes described herein, M is cobalt. In certain embodiments of porphyrin and phthalocyanine-based complexes described herein, M is manganese.

[0320] In certain embodiments, porphyrin complexes of the present invention include, but are not limited to those in Table 2 below:

TABLE-US-00004 TABLE 2 [00245] [00246] [00247] [00248] [00249] [00250] [00251] [00252] [00253] [00254] [00255] [00256] [00257] [00258] [00259] [00260] [00261] [00262]

[0321] In certain embodiments, for complexes of Table 2, M is CoX, where X is as defined above. In certain embodiments, for complexes of Table 2, M is CoOC(O)CF.sub.3. In certain embodiments, for complexes of Table 2, 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 2, M is CoN.sub.3. In certain embodiments, for complexes of Table 2, M is CoCl. In certain embodiments, for complexes of Table 2, M is Co-nitrophenoxy. In certain embodiments, for complexes of Table 2, M is Co-dinitrophenoxy.

[0322] In certain embodiments, for complexes of Table 2, M is AlX, where X is as defined above. In certain embodiments, for complexes of Table 2, M is CrX, where X is as defined above.

[0323] In certain embodiments, porphyrin complexes of the present invention are synthesized as shown in the following schemes:

##STR00263## ##STR00264##

[0324] In some embodiments, the present disclosure provides methods of polymerization comprising contacting an epoxide with carbon dioxide in the presence of a provided metal complex to form a polycarbonate. In some embodiments, the present invention provides a method of polymerization, the method comprising: [0325] a) providing an epoxide of formula:

##STR00265## [0326] wherein: [0327] 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 [0328] 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; [0329] 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; [0330] 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:

##STR00266##

[0331] In some embodiments, a provided polymer has a formula:

##STR00267##

In some embodiments, a provided polymer has a formula:

##STR00268##

In some embodiments, carbon dioxide is optional and a provided polymer has a formula:

##STR00269##

[0332] 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. In some embodiments, the epoxide is ethylene oxide, propylene oxide, or cyclohexene oxide.

[0333] 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.

[0334] 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.

[0335] 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.

[0336] 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.

[0337] 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.

[0338] 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.

[0339] 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.

[0340] 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.

[0341] 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.

[0342] 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.

[0343] 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.

[0344] 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.

[0345] 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.

[0346] In certain embodiments, R.sup.a is selected from methyl, ethyl, propyl, butyl, vinyl, allyl, phenyl, trifluoromethyl,

##STR00270##

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

##STR00271##

In certain embodiments, R.sup.a is

##STR00272##

In certain embodiments, R.sup.a is

##STR00273##

In certain embodiments, R.sup.a is

##STR00274##

In certain embodiments,

R.SUP.a is

[0347] ##STR00275##

In certain embodiments, R.sup.a

##STR00276##

In certain embodiments, R.sup.a is

##STR00277##

[0348] 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.

[0349] In some embodiments, R.sup.c is hydrogen. In some embodiments, R.sup.c is optionally substituted C.sub.1-12 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.

[0350] 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.

[0351] 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.

[0352] 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.

[0353] 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.

[0354] In some embodiments, the invention includes methods for synthesizing cyclic carbonates from carbon dioxide and epoxides using catalysts 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

[0355] A general route to a symmetric cobalt (III) salen ligand of the present invention is shown in Schemes E1 and E2, below:

##STR00278##

[0356] As shown in Scheme E1, disubstituted phenol E1-a is formylated to provide salicylaldehyde derivative E1-b. Two equivalents of this aldehyde are then reacted with a diamine (in this case 1,2-diamino cyclohexane) to afford Schiff base E1-c. This compound is then reacted with cobalt (II) acetate to give the Co(II)-salen complex (not shown) which is oxidized by air in the presence of trifluoroacetic acid to afford the active cobalt (III) catalyst. Similar chemistries can be applied to synthesis of the catalysts described hereinabove. One skilled in the art of organic synthesis can adapt this chemistry as needed to provide the specific catalysts described herein.

Example 2

[0357] A typical route to an asymmetric cobalt (III) salen ligand is shown in Scheme E2:

##STR00279##

[0358] As shown in Scheme E2, disubstituted salicylaldehyde derivative E1-b is treated with one equivalent of a monohydrochloride salt of 1,2 cyclohexanediamine. the resulting Schiff base E2-a is then neutralized and a second different salicylaldehyde derivative is added. This compound is then reacted with cobalt (II) acetate to give the Co(II)-salen complex which is oxidized by air in the presence of trifluoroacetic acid to afford the active cobalt (III) catalyst. Similar chemistries can be applied to synthesis of the catalysts described hereinabove. One skilled in the art of organic synthesis can adapt this chemistry as needed to provide the specific catalysts described herein.

Example 3

[0359] Example 3 describes the synthesis of a catalyst

##STR00280##

where M is Co(II),

##STR00281##

is salcy, is

##STR00282##

Z is a P-linked phosphorimine moiety

##STR00283##

and m is 1, wherein there are one or two (Z).sub.m groups present (Scheme E4 and E3, respectively).

##STR00284##

[0360] As shown in Scheme E3, triol E3-a is protected as a ketal to afford monohydric alcohol E3-b, this compound is then alkylated with bromide E3-c to afford benzyl ether E3-d. Deprotection and oxidation of the other benzylic alcohol affords salicylaldehyde E3-e which is condensed with cyclohexanediamine as described above to give ligand E3-f. The phosphorimine nitrogen is then quaternized and the metal complex formed as before to provide catalyst E3-h. In an alternative route not shown here the metal is first inserted and then quaternization is performed.

##STR00285##

[0361] As shown in Scheme E3b, salicyladedyde E3-e (described above) is condensed with cyclohexanediamine monohydrochloride to afford the mono-Schiff base hydrochloride E4a. This salt is then neutralized, condensed with di-t-butyl salicaldehyde, and methylated to give E4-b. The resulting ligand is metallated and oxidized as described above for Scheme E3 to give catalyst E4-c.

Example 4

[0362] Example 4 describes the synthesis of catalysts where M is Co(III),

##STR00286##

is salcy, is

##STR00287##

Z is a 1-[4-dimethylamino-pyridinium]

##STR00288##

or 1-[N-methylimidazolium],

[0363] ##STR00289##

and m is 1, wherein there are one or two (Z).sub.m groups present (Scheme E5 and E6, respectively).

##STR00290##

[0364] Scheme E4 shows the synthesis of compounds CS-6 and CS-7. For each compound trans-1,2-Diaminocyclohexane (2.0 mol) is slowly added to an anhydrous ethanol solution of benzyl chloride CS-4 (1.0 mol). The reaction is stirred and heated to reflux for 3 h, then cooled to rt and diluted with water. This mixture is cooled overnight in the freezer and solids are collected by filtration to afford dichloride CS-5. The dichloride CS-5 (1.0 mol) is reacted with N,N-Dimethylamino pyridine (2.0 mol) or N-methyl imidazole in acetonitrile. The reactions are heated at 80 C. for 18 h and then the solvent is removed in vacuo to provide the respective ammonium salts. These salts are metallated and oxidized as described previously to provide catalysts CS-6 and CS-7.

Example 5

[0365] Example 5 describes the synthesis of catalysts where M is Co(III),

##STR00291##

is salcy, is

##STR00292##

Z is a 1-[N-methylimidazolium] (CS-8), or dimethylamino (CS-9) and m is 1, wherein there are two (Z).sub.m groups present (Scheme E5 and E6, respectively).

##STR00293##

[0366] Scheme E5 shows the synthesis of compounds CS-8 and CS-9 using conditions similar to those described above. Synthesis of CS-8: The known compound 1-(2-methylaminoethyl)-3-methylimidazole (2.0 mol) is combined with CS-5 (1.0 mol) in acetonitrile. The reaction is heated to 80 C. for 18 h and then the solvent is removed in vacuo, metallation with Co(OAc).sub.2 and oxidation in TFA are then performed as described above to afford catalyst CS-8. Synthesis of CS-9: N,N,N-Trimethyl-1,2-ethanediamine (4.0 mol) is combined with CS-5 (1.0 mol) in acetonitrile. The reaction is heated to 80 C. for 18 h, cooled, and the solvent is removed in vacuo. The crude product is diluted with ether, filtered to remove amine salts, and concentrated in vacuo. The residue is dissolved in degassed methanol and combined with Co(OAc).sub.2 (1.0 mol). After stirring for 3 h the residue is filtered and washed with methanol. Trifluoroacetic acid (1.0 mol) is added slowly to a stirring solution of the solid residue in dichloromethane. After stirring open to air for 3 h, the solids are filtered and dried in vacuo to produce CS-9.

Example 6

[0367] Example 6 and Scheme E6 describe the synthesis of catalysts where M is Co(III),

##STR00294##

is salcy, is

##STR00295##

Z is dibutylamino and in is 1, wherein there are two (Z).sub.m groups present.

##STR00296##

[0368] Synthesis of CS-10:

[0369] Ligand CS-5 (1.0 mol), 3-(dibutylamino)-1-propanol (2.0 mol), a 50% NaOH solution (10 mol), tetrabutylammonium bisulphate (4 mol %), and dichloromethane are combined and heated at 65 C. overnight. The reaction mixture is concentrated in vacuo to remove the bulk of the solvent and the aqueous layer is extracted with ethyl acetate. The organic layer is separated, dried with magnesium sulfate, filtered, and concentrated in vacuo. After purification using silica gel the product is dissolved in degassed methanol and combined with Co(OAc).sub.2 (1.0 mol). After stirring for 3 h, the residue is filtered and washed with methanol. Trifluoroacetic acid (1.0 mol) is added slowly to a dichloromethane solution of the solid residue. After stirring open to air for 3 h, the solids are filtered and dried in vacuo to produce CS-10.

Example 7

[0370] Example 7 and Scheme E7 describe the synthesis of catalysts where M is Co(III),

##STR00297##

is salcy, includes two

##STR00298##

groups taken together to form a ring including the Z group, Z is 3-[N-methylpyridinium] and m is 1, wherein there is one (Z).sub.m group present.

##STR00299##

[0371] Synthesis of CS-11.

[0372] Ligand CS-5 (1.0 mol), 3,5-bis(hydroxymethyl)-N-methylpyridinium iodide (2.0 mol), a 50% NaOH solution (10 mol), tetrabutylammonium bisulphate (4 mol %), and dichloromethane are combined and heated at 65 C. overnight. The reaction mixture is concentrated in vacuo to remove the bulk of the solvent and the aqueous layer is extracted with ethyl acetate. The organic layer is separated, dried with magnesium sulfate, filtered, and concentrated in vacuo. The procedure detailed above for the metallation and oxidation is followed to produce CS-11.

Example 8

[0373] Example 8 and Scheme E8 describe the synthesis of catalysts where M is Co(III),

##STR00300##

is salcy, is

##STR00301##

Z is 1-[4-t-butylpyridinium], and m is 2, wherein there are two (Z).sub.m groups present.

##STR00302##

[0374] Synthesis of AC-2.

[0375] Intermediate AC-1 (0.37 g, 0.35 mmol), 4-tbutylpyridine (0.21 mL, 1.41 mmol), and AcCN (4 mL) were combined in a sealed vial and heated to 80 C. with stirring for 18 h. The solvent was removed in vacuo, leaving a yellow residue (0.61 g, 110% yield, AcCN present). .sup.1H NMR (400 MHz, CDCl.sub.3, ): 9.53 (t, 8H), 8.21 (s, 2H), 7.94 (t, 8H), 7.08 (s, 2H), 6.83 (s, 2H), 4.81 (m, 8H), 3.29 (m, 2H), 2.78 (m, 2H), 2.15 (s, 6H), 1.5-2.0 (m, 24H), 1.36 (s, 36H); IR (ATR, film cast from AcCN): .sub.CN=1637 cm.sup.1. A solution of the residue (0.30 g, 0.19 mmol) in dry EtOH (5 mL) was added to AgBF.sub.4 (0.19 g, 0.85 mmol) in a schlenk tube and stirred overnight shielded from the light. The solution was filtered through Celite and the solvent was removed in vacuo, giving a solid residue. This residue was flashed over a small plug of silica gel with 5:1 CH.sub.2Cl.sub.2:EtOH as eluant. The solvent was removed to give a solid residue (0.18 g, 67% yield). .sup.1H NMR (400 MHz, CDCl.sub.3, ): 8.75 (t, 8H), 7.98 (d, 2H), 7.92 (t, 8H), 7.1-7.3 (m, 4H), 4.52 (m, 8H), 3.6 (m, 2H), 2.7 (m, 2H), 2.19 (s, 6H), 1.5-2.0 (m, 24H), 1.38 (s, 36H); IR (ATR, film cast from CH.sub.2Cl.sub.2): .sub.CN=1641 cm.sup.1, .sub.BF.sub.4=1050 cm.sup.1. A solution of the residue (0.18 g, 0.12 mmol) in dry EtOH (4 mL) was added to Co(OAc).sub.2 (0.022 g, 0.12 mmol) in a schlenk tube under N.sub.2. The solution was stirred for 3 h at room temperature, and the solvent was removed in vacuo. The residue was triturated with ether, dried in vacuo, and redissolved in CH.sub.2Cl.sub.2. A solution of CF.sub.3CO.sub.2H (9 L, 0.12 mmol) in CH.sub.2Cl.sub.2 (80 L) was added and the solution stirred for 3 h open to air. Solid NaO.sub.2CCF.sub.3 (0.067 g, 0.49 mmol) was added, and the solution was stirred under N.sub.2 for 2 days. The solution was filtered through Celite and the solvent was removed in vacuo to leave a brown residue (0.071 g, 37% yield). .sup.1H NMR (400 MHz, DMSO-d.sub.6, ): 8.86 (t, 8H), 8.08 (t, 8H), 8.07 (s, 2H), 7.30 (m, 4H), 4.44 (m, 8H), 3.54 (m, 2H), 2.9 (m, 2H), 2.47 (s, 6H), 1.5-2.0 (m, 24H), 1.29 (s, 36H); IR (ATR): .sub.CO=1682 cm.sup.1, .sub.CN=1641 cm.sup.1.

[0376] Additional ligands AC-6 through AC-11 were synthesized using the conditions described for compound AC-2 and are summarized in Scheme E8b and Table E8:

TABLE-US-00005 TABLE E8 Scheme E8b [00303] Q Compound (Scheme E8b) .sup.1H NMR spectra.sup.a (, ppm) IR.sup.b (cm.sup.1) AC-6.sup.c [00304] 9.0 (d, 8H), 8.6 (t, 4H), 8.5 (s, 2H), 8.1 (t, 8H), 6.9 (s, 2H), 6.8 (s, 2H), 4.5 (t, 8H), 3.4 (m, 2H), 2.1 (s, 6H), 1.4-2.9 (m, 24H). .sub.CN = 1629 AC-7 [00305] 8.61 (d, 8H), 8.29 (s, 2H), 6.99 (s, 2H), 6.92 (d, 8H), 6.85 (s, 2H), 4.30 (t, 8H), 3.34 (m, 2H), 3.23 (s, 24H), 2.65 (m, 2H), 2.18 (s, 6H), 1.4-2.9 (m, 16H). .sub.CN = 1649 AC-8 [00306] .sub.CN = 1627 AC-9 [00307] .sub.CN = 1610 AC-10 [00308] .sub.CN = 1627 AC-11 [00309] .sub.CN = 1628 .sup.400 MHz, CDCl.sub.3. .sup.bAll compounds exhibited the loss of a peak at 1213 cm.sup.1 attributed to the CH.sub.2I group in AC-1. .sup.cNMR spectrum is in DMSO-d.sub.6.

Example 9

[0377] Example 9 and Scheme E9 describe the synthesis of catalysts where M is Co(III),

##STR00310##

is salcy, is

##STR00311##

Z is N,N-bis-(3-dimethylaminopropyl)amino (AC-4), tetramethyl guanidino (AC-5), N-linked morpholino (AC-6), or N-linked piperidino (AC-14), and m is 2, wherein there are two (Z).sub.m groups present.

##STR00312##

[0378] Synthesis of AC-4.

[0379] Intermediate AC-3 (0.45 g, 0.63 mmol), 3,3-iminobis(N,N-dimethylpropylamine) (0.28 mL, 1.26 mmol), K.sub.2CO.sub.3 (0.35 g, 2.52 mmol) and AcCN (5 mL) were combined in a sealed vial and heated to 80 C. with stirring for 18 h. The solution was filtered and the solvent was removed in vacuo, triturated with ether, and dried in vacuo to leave a yellow residue (0.48 g, 91% yield). .sup.1H NMR (400 MHz, CDCl.sub.3, ): 8.21 (m, 2H), 6.8-7.2 (m, 4H), 3.75 (m, 2H), 3.0-3.4 (m, 20H), 2.0-2.8 (m, 28H), 2.18 (s, 6H), 1.4-2.0 (m, 24H); IR (ATR): .sub.CN=1600 cm.sup.1. A solution of the residue (0.21 g, 0.25 mmol) in dry EtOH (10 mL) was added to Co(OAc).sub.2 (0.045 g, 0.25 mmol) in a schlenk tube under N.sub.2. CH.sub.2Cl.sub.2 (3 mL) was added to completely dissolve the solution. The solution was stirred for 18 h at room temperature, and the solvent was removed in vacuo. The residue was triturated with ether, dried in vacuo, and redissolved in CH.sub.2Cl.sub.2 (10 mL). CF.sub.3CO.sub.2H (20 L, 0.25 mmol) was added and the solution stirred for 3.5 h open to air. The solvent was removed in vacuo, triturated with ether, and dried in vacuo to leave a brown residue (0.28 g, 108% yield, residual CH.sub.2Cl.sub.2). .sup.1H NMR (400 MHz, DMSO-d.sub.6, ): 7.92 (m, 2H), 7.1-7.4 (m, 4H), 3.58 (m, 2H), 3.0-3.4 (m, 20H), 2.0-2.8 (m, 28H), 2.3 (s, 6H), 1.4-2.0 (m, 24H); IR (ATR): .sub.CO=1688 cm.sup.1, .sub.CN=1616 cm.sup.1.

[0380] Synthesis of AC-5.

[0381] Intermediate AC-3 (0.20 g, 0.29 mmol), 1,1,3,3-tetramethylguanidine (0.21 mL, 1.71 mmol), K.sub.2CO.sub.3 (0.39 g, 2.85 mmol) and AcCN (2 mL) were combined in a sealed vial and reacted as in AC-4, except that the residue was also washed with hexanes. .sup.1H NMR (400 MHz, CDCl.sub.3, ): 8.23 (d, 2H), 6.95 (s, 2H), 6.80 (s, 2H), 3.35 (m, 2H), 3.1 (m, 4H), 2.7-2.8 (m, 24H), 2.48 (m, 4H), 2.20 (s, 6H), 1.4-2.0 (m, 16H); IR (ATR): .sub.CN=1594 cm.sup.1. The residue was reacted as in AC-4. TR (ATR): .sub.CO=1690 cm.sup.1, .sub.CN=1610 cm.sup.1.

[0382] Synthesis of AC-6.

[0383] Intermediate AC-3 (0.32 g, 0.44 mmol), morpholine (0.16 mL, 1.77 mmol), K.sub.2CO.sub.3 (0.61 g, 4.4 mmol) and AcCN (4 mL) were combined in a sealed vial and reacted as in AC-4, except that the residue was also washed with a NaOAc buffer (pH=4) solution to remove residual morpholine. .sup.1H NMR (400 MHz, CDCl.sub.3, ): 8.22 (s, 2H), 6.92 (s, 2H), 6.79 (s, 2H), 3.69 (m, 8H), 3.28 (m, 2H), 2.2-2.5 (m, 16H), 2.19 (s, 6H), 1.4-2.0 (m, 16H). The residue was reacted as in AC-4. .sup.1H NMR (400 MHz, DMSO-d.sub.6, ): 7.91 (s, 2H), 7.23 (s, 2H), 7.14 (s, 2H), 3.6 (m, 2H), 3.52 (m, 8H), 2.99 (m, 2H), 2.57 (s, 6H), 2.47 (m, 4H), 2.2-2.5 (m, 12H), 1.4-2.0 (m, 16H); IR (ATR): .sub.CO=1671 cm.sup.1, .sub.CN=1630 cm.sup.1.

[0384] Additional ligands AC-13 and AC-14 were synthesized using the conditions described for compounds AC-4 through AC-6 and are summarized in Scheme E9b and Table E9:

##STR00313##

TABLE-US-00006 TABLE E9 Q Compound (Scheme E9b) .sup.1H NMR spectra.sup. (, ppm) IR.sup.b (cm.sup.1) AC-13 [00314] 8.25 (s, 2H), 7.02 (d, 2H), 6.77 (d, 2H), 3.7 (m, 8H), 3.3 (m, 2H), 2.2-2.6 (m, 12H), 1.3-2.0 (m, 20H), 1.37 (s, 18H) .sub.CN = 1628 AC-14 [00315] .sub.CN = 1629 .sup.400 MHz, CDCl.sub.3. .sup.bAll compounds exhibited the loss of a peak at 1213 cm.sup.1 attributed to the CH.sub.2I group in AC-1.

Example 10

[0385] Confirmation of inventive concepts, processes, methods, and compositions described herein has been provided, among other ways, through publication by others after the priority date of the present case. For example, Examples 10-27 describe working Examples presented in Chinese Patent Application No. 200810229276.1, published as CN 101412809A. Additional experimental and characterization data are described by Lu and co-workers, J. Am. Chem. Soc., 2009, 131, 11509-11518, and supporting information available at www.pubs.acs.org, the entirety each of which is hereby incorporated by reference.

[0386] In certain embodiments, provided catalysts and/or methods for the preparation of polycarbonate are characterized by one or more of the following: retaining high catalytic activity at low catalyst concentration; reaction conditions that are relatively mild; high catalytic activity with high selectivity for polymer product; alternate structure in the polycarbonate product higher than 97% with relatively narrow distribution of molecular weight; retaining high catalytic activity for copolymerization of carbon dioxide and epoxides at higher reaction temperatures (e.g., above 50 C., above 75 C., or above 100 C.); and catalysts that can be used to catalyze the polymerization of carbon dioxide with two or more alkylene oxides for the synthesis of polycarbonate polymer.

[0387] The following materials were added sequentially into a stainless steel high pressure reactor of effective volume of 200 mL at ambient temperature: 0.1 mmole of cobalt complex I-a (R.sub.1 is cyclohexyl diamine, X is NO.sub.3.sup.1 anion; R.sub.2H; R.sub.3, R.sub.4 and R.sub.5 are tertiary butyl; group containing organic base group is at position 3 of the benzene ring in the ligand, n is 2) and one mole of propylene oxide. The reactor was then filled with carbon dioxide and the pressure is maintained constant at 2.0 MPa. The temperature was controlled at 25 C. The content was stirred with a magnetic stirring bar for 6 hours and the remaining carbon dioxide was slowly released. The remaining alkylene oxide was collected in 20 C. cold trap and a certain amount of mixture of methanol/chloroform was added to dissolve the high polymer. Then a large amount of diethyl ether was added to precipitate the polycarbonate. The precipitate was filtered and washed several times with diethyl ether and dried in vacuum to constant weight to afford 27 grams of polycarbonate as a white solid. The average molecular weight of the polymer was determined by gel permeation chromatography to be 101,000 g/mol with a molecular weight distribution of 1.24. A Varian INOVA-400 MHz Nuclear Magnetic Resonance spectrometer was used to determine its .sup.1H-NMR and the result showed that the alternate structure is over 99%.

##STR00316##

Example 11

[0388] The same equipment and reaction conditions were employed as in Example 10 with the same catalyst and the same conditions except that the molar ratio of catalyst to propylene oxide was changed from 1:10000 to 1:50000 (0.02 mmole of catalyst and 1 mole of propylene oxide were used). The reaction was carried out at 25 C. for 24 hours to afford 21 grams of poly(propylene carbonate) with a molecular weight of 223,000 g/mol and a molecular weight distribution of 1.29. The polymer formed contained more than 99% carbonate linkages.

Example 12

[0389] The same equipment and reaction conditions were employed as in Example 10 with the same catalyst and the same conditions except that the molar ratio of catalyst to propylene oxide was changed from 1:10000 to 1:200000 (0.008 mmole of catalyst and 1.6 mole of propylene oxide were used). The reaction was carried out at 50 C. for 10 hours to afford 19 grams of poly(propylene carbonate) with a molecular weight of 318,000 g/mol and a molecular weight distribution of 1.37. The polymer formed contained more than 99% carbonate linkages.

Example 13

[0390] The same equipment and reaction conditions were employed as in Example 10 with the same catalyst and the same conditions except that the molar ratio of catalyst to propylene oxide was changed from 1:10000 to 1:2000 (0.5 mmole of catalyst and 1 mole of propylene oxide were used). The reaction was carried out at 25 C. for 3 hours to afford 48 grams of poly(propylene carbonate) with a molecular weight of 52,800 g/mol and a molecular weight distribution of 1.30. The polymer formed contained more than 99% carbonate linkages.

Example 14

[0391] The same equipment and reaction conditions were employed as in Example 10 with the same catalyst and the same conditions except that the reaction temperature was changed from 25 C. to 100 C. and the reaction was carried out for 0.5 hours to afford 34 grams of poly(propylene carbonate) with a molecular weight of 112,400 g/mol and a molecular weight distribution of 1.38. The polymer formed contained more than 99% carbonate linkages.

Example 15

[0392] The same equipment and reaction conditions were employed as in Example 10 with the same catalyst and the same conditions except that the reaction temperature was changed from 25 C. to 10 C. and the reaction was carried out for 10 hours to afford 18 grams of poly(propylene carbonate) with a molecular weight of 914,000 g/mol and a molecular weight distribution of 1.38. The polymer formed contained more than 99% carbonate linkages.

Example 16

[0393] The same equipment and reaction conditions were employed as in Example 10 with the same catalyst and the same conditions except that the propylene oxide was replaced with 1,2-butylene oxide. The reaction was carried out at 25 C. for 6 hours to afford 31 grams of poly(butylene carbonate) with a molecular weight of 127,000 g/mol and a molecular weight distribution of 1.21. The polymer formed contained more than 99% carbonate linkages.

Example 17

[0394] The same equipment and reaction conditions were employed as in Example 10 with the same catalyst and the same conditions except that the propylene oxide was replaced with 1,2-octylene oxide. The reaction was carried out at 25 C. for 10 hours to afford 34 grams of poly(octylene carbonate) with a molecular weight of 109,000 g/mol and a molecular weight distribution of 1.38. The polymer formed contained more than 99% carbonate linkages.

Example 18

[0395] The same equipment and reaction conditions were employed as in Example 10 with the same catalyst and the same conditions except that the propylene oxide was replaced with a mixture of propylene oxide and cyclohexylene oxide (the molar ratio of the catalyst to propylene oxide and cyclohexylene oxide was 1:5000:5000). The reaction was carried out at 50 C. for 6 hours to afford 59 grams of poly(propylene-co-cylcohexene carbonate) with a molecular weight of 187,000 g/mol and a molecular weight distribution of 1.29. The polymer formed contained more than 99% carbonate linkages.

Example 19

[0396] The same equipment and reaction conditions were employed as in Example 10 with the same catalyst and the same conditions except that the axial anion in the cobalt complex I-a was changed from nitrate radical to acetate moiety. The reaction was carried out at 25 C. for 6 hours to afford 34 grams of poly(propylene carbonate) with a molecular weight of 95,000 g/mol and a molecular weight distribution of 1.28. The polymer formed contained more than 99% carbonate linkages.

Example 20

[0397] The same equipment and reaction conditions were employed as in Example 10 with the same catalyst and the same conditions except that the diamine skeleton in the cobalt complex I-a was changed from cyclohexane diamine to ethylene diamine. The reaction was carried out at 25 C. for 6 hours to afford 29 grams of poly(propylene carbonate) with a molecular weight of 112,000 g/mol and a molecular weight distribution of 1.20. The polymer formed contained more than 99% carbonate linkages.

Example 21

[0398] The same equipment and reaction conditions were employed as in Example 10 with the same catalyst and the same conditions except that the diamine skeleton in the cobalt complex I-a was changed from cyclohexane diamine to o-phenylene diamine. The reaction was carried out at 25 C. for 6 hours to afford 25 grams of poly (propylene carbonate) with a molecular weight of 92,000 g/mol and a molecular weight distribution of 1.15. The polymer formed contained more than 99% carbonate linkages.

Example 22

[0399] The following materials were added sequentially into a stainless steel high pressure reactor of volume of 200 mL at ambient temperature: 0.1 mmole of cobalt complex 1-b (R.sub.1 is 1,2-propylene diamine, X is dinitrophenyl anion; R.sub.2H; R.sub.1 is tertiary butyl; there are organic base groups at position 5 of the two benzene rings in the ligand, n is 0) and 1 mole of propylene oxide. The reactor was then filled with carbon dioxide and the pressure was maintained constant at 2.0 MPa. The reaction was carried out at 25 C. for 6 hours to afford 23 grams of polycarbonate as a white solid. The average molecular weight of the polymer was determined by gel permeation chromatography to be 81,000 g/mol with a molecular weight distribution of 1.34. The polymer formed contained more than 99% carbonate linkages.

##STR00317##

Example 23

[0400] The following materials were added sequentially into a stainless steel high pressure reactor of volume of 200 mL at ambient temperature: 0.1 mmole of cobalt complex I-c (R.sub.1 is ethylene diamine, X is dinitrophenyl anion; R.sub.2H; R.sub.3 is tertiary butyl; there are organic base groups at position 3 and position 5 of one of the benzene rings in the ligand, n is 0) and 1 mole of propylene oxide. The reactor was then filled with carbon dioxide and the pressure was maintained constant at 2.0 MPa. The reaction was carried out at 25 C. for 6 hours to afford 23 grams of polycarbonate as a white solid. The average molecular weight of the polymer was determined by gel permeation chromatography to be 81,000 g/mol with a molecular weight distribution of 1.34. The polymer formed contained more than 99% carbonate linkages.

##STR00318##

Example 24

[0401] The following materials are added sequentially into a stainless steel high pressure reactor of volume of 200 mL at ambient temperature: 0.1 mmole of cobalt complex I-b (R.sub.1 is ethylene diamine, X is dinitrophenyl anion; R.sub.2H; R.sub.3 and R.sub.4 are tertiary butyl; there are organic base groups at position 5 of the two benzene rings in the ligand, n is 0) and 1 mole of propylene oxide. The reactor was then filled with carbon dioxide and the pressure was maintained constant at 2.0 MPa. The reaction was carried out at 25 C. for 6 hours to afford 26 grams of polycarbonate as a white solid. The average molecular weight of the polymer was determined by gel permeation chromatography to be 83,000 g/mol with a molecular weight distribution of 1.19. The polymer formed contained more than 99% carbonate linkages. The polymer formed contained more than 99% carbonate linkages.

Example 25

[0402] The following materials are added sequentially onto a stainless steel high pressure reactor of volume of 200 mL at ambient temperature: 0.1 mmole of cobalt complex I-a (R.sub.1 is 2,3-butylene diamine, X is nitrate anion; R.sub.2H; R.sub.3 and R.sub.4 are methoxyl group; R.sub.1 is tertiary butyl; there is an organic base group at position 3 of one of the benzene rings in the ligand, n is 2) and 1 mole of propylene oxide. The reactor was then filled with carbon dioxide and the pressure is maintained constant at 2.0 MPa. The reaction was carried out at 25 C. for 6 hours to afford 22 grams of polycarbonate as a white solid. The average molecular weight of the polymer was determined by gel permeation chromatography to be 73,000 g/mol with a molecular weight distribution of 1.14. The polymer formed contained more than 99% carbonate linkages.

Example 26

[0403] The same equipment and reaction conditions were employed as in Example 10 with the same catalyst and the same conditions except that the pressure was changed from 2.0 MPa to 0.1 MPa. The reaction was carried out at 25 C. for 10 hours to afford 25 grams of poly(propylene carbonate) with a molecular weight of 100,400 g/mol and a molecular weight distribution of 1.17. The polymer formed contained more than 99% carbonate linkages.

Example 27

[0404] The same equipment and reaction conditions were employed as in Example 10 with the same catalyst and the same conditions except that the pressure was changed from 2.0 MPa to 6.0 MPa. The reaction was carried out at 25 C. for 6 hours to afford 29 grams of poly(propylene carbonate) with a molecular weight of 125,000 g/mol and a molecular weight distribution of 1.25. The polymer formed contained more than 99% carbonate linkages.

TABLE-US-00007 TABLE E10 Summary of Examples 10-27. Reaction Conditions Catalyst Cat. Epoxide P T t Ex Cat R1 R2 R3 R4 R5 X n (mmol) (mg) (mmol) MPa psi (deg C.) (h) 10 I-a Cy H tBu tBu tBu NO.sub.3 2 PO 0.1 70.5 1000 2 290 25 6 11 0.02 14.1 1000 2 290 25 24 12 0.008 5.64 1600 2 290 50 10 13 0.5 353 1000 2 290 25 3 14 0.1 70.5 1000 2 290 100 0.5 15 0.1 70.5 1000 2 290 10 10 26 0.1 70.5 1000 0.1 15 25 10 27 0.1 70.5 1000 6 870 25 6 16 BO 0.1 70.5 1000 2 290 25 6 17 OO 0.1 70.5 1000 2 290 25 10 18 PO/CHO 0.1 70.5 1000 2 290 50 6 19 Cy H tBu tBu tBu OAc 2 PO 0.1 70.2 1000 2 250 25 6 20 En H tBu tBu tBu NO.sub.3 2 PO 0.1 65.1 1000 2 290 25 6 21 Ph H tBu tBu tBu NO.sub.3 2 PO 0.1 69.9 1000 2 290 25 6 25 Bu H OMe OMe tBu NO.sub.3 2 PO 0.1 62.7 1000 2 290 25 6 22 I-b Pr tBu DNP 0 PO 0.1 89 1000 2 290 25 6 24 I-b En H tBu DNP 0 PO 0.1 87.7 1000 2 290 25 6 23 I-c En H tBu tBu DNP 0 PO 0.1 88.2 1000 2 290 25 6 Results Catalyst PPC TOF MW g PC/ kg PC/ Ex Cat R1 R2 R3 R4 R5 X n yield (g) conv. (%) TON (h.sup.1) (kDa) PDI g Cat mol Cat. 10 I-a Cy H tBu tBu tBu NO.sub.3 2 27 26.4 2644 441 101 1.2 383 270 11 21 20.6 10284 429 233 1.3 1489 1050 12 19 11.6 23262 2326 318 1.4 3369 2375 13 48 47.0 940 313 53 1.3 136 96 14 34 33 3330 6660 112 1.4 482 340 15 18 17.6 1763 176 914 1.4 255 180 26 25 24.5 2449 244.9 100 1.2 355 250 27 29 28.4 2840 473.4 125 1.3 411 290 16 31 26.7 2669 444.9 127 1.2 440 310 17 34 19.7 1974 197.4 109 1.4 482 340 18 59 837 590 19 Cy H tBu tBu tBu OAc 2 34 33.3 3330 555 95 1.3 484 340 20 En H tBu tBu tBu NO.sub.3 2 29 28.4 2840 473 112 1.2 446 290 21 Ph H tBu tBu tBu NO.sub.3 2 25 24.5 2449 408 92 1.2 358 250 25 Bu H OMe OMe tBu NO.sub.3 2 22 21.5 2155 359.1 73 1.1 351 220 22 I-b Pr tBu DNP 0 23 22.5 2253 375 81 1.3 258 230 24 I-b En H tBu DNP 0 26 25.5 2547 424.4 83 1.2 296 260 23 I-c En H tBu tBu DNP 0 23 22.5 2253 375.4 81 1.3 261 230

[0405] 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.