CATALYTIC CARBONYLATION CATALYSTS AND METHODS

Abstract

In one aspect, the present invention provides catalysts for the carbonylation of heterocycles. The inventive catalysts feature metal-ligand complexes having cationic functional groups tethered to the ligand, wherein the tethered cationic groups are associated with anionic metal carbonyl species. The invention also provides methods of using the inventive catalysts to affect the ring opening carbonylation of epoxides.

Claims

1. A catalyst for the carbonylation of heterocycles comprising the combination of: i) one or more cationic functional moieties, where each cationic functional moiety comprises a linker and 1 to 4 cationic functional groups; ii) one or more ligands to which at least one cationic functional moiety is covalently tethered wherein the one or more ligand(s) are coordinated to one or two metal atoms; and iii) at least one anionic metal carbonyl species associated with a cation present on the metal complex.

2. The catalyst of claim 1, wherein the one or more ligands to which at least one cationic functional moiety is covalently tethered is selected from the group consisting of porphryin ligands and salen ligands.

3. The catalyst of claim 2, wherein catalyst comprises a salen or porphyrin complex of a metal selected from the group consisting of: Zn(II), Cu(II), Mn(II), Co(II), Ru(II), Fe(II), Co(II), Rh(II), Ni(II), Pd(II), Mg(II), Al(III), Cr(III), Cr(IV), Ti(IV), Fe(III), Co(III), Ti(III), In(III), Ga(III), Mn(III).

4. The catalyst of claim 2, wherein the catalyst comprises a salen or porphyrin complex of aluminum.

5. The catalyst of claim 2, wherein the catalyst comprises a salen or porphyrin complex of chromium.

6. The catalyst of claim 1, wherein the one or more cationic functional groups comprise onium salts.

7. The catalyst of claim 1, wherein the onium salts comprise at least one of nitrogen and phosphorous.

8. The catalyst of claim 1, wherein the one or more cationic functional groups are selected from the group consisting of: ##STR00330## ##STR00331## ##STR00332## or a combination of two or more of these, wherein: each 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; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle; a 7- to 14-membered saturated or partially unsaturated polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; an 8- to 14-membered polycyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated monocyclic heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 14-membered saturated or partially unsaturated polycyclic heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; phenyl; or an 8- to 14-membered polycyclic aryl ring; wherein R.sup.1 and R.sup.2 can be taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more additional heteroatoms; each 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; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle; a 7- to 14-membered saturated or partially unsaturated polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; an 8- to 14-membered polycyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated monocyclic heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 14-membered saturated or partially unsaturated polycyclic heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; phenyl; or an 8- to 14-membered polycyclic aryl ring; wherein an R.sup.3 group can be taken with an R.sup.1 or R.sup.2 group to form one or more optionally substituted rings; and R.sup.5 is R.sup.2 or hydroxyl; wherein R.sup.1 and R.sup.5 can be taken together with intervening atoms to form one or more optionally substituted carbocyclic, heterocyclic, aryl, or heteroaryl rings; each R.sup.6 and R.sup.7 is independently hydrogen or an optionally substituted radical selected from the group consisting of C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle; a 7- to 14-membered saturated or partially unsaturated polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; an 8- to 14-membered polycyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated monocyclic heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 14-membered saturated or partially unsaturated polycyclic heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; phenyl; or an 8- to 14-membered polycyclic aryl ring; wherein R.sup.6 and R.sup.7 can be taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more heteroatoms, and an R.sup.6 and R.sup.7 group can be taken with an R.sup.1 or R.sup.2 group to form one or more optionally substituted rings; each occurrance of R.sup.8 is independently selected from the group consisting of: halogen, NO.sub.2, CN, SR.sup.y, S(O)R.sup.y, S(O).sub.2R.sup.y, NR.sup.yC(O)R.sup.y, OC(O)R.sup.y, CO.sub.2R.sup.y, NCO, 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; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle; a 7- to 14-membered saturated or partially unsaturated polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; an 8- to 14-membered polycyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated monocyclic heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 14-membered saturated or partially unsaturated polycyclic heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; phenyl; or an 8- to 14-membered polycyclic aryl ring; wherein each R.sup.y is independently as defined above and described in classes and subclasses herein, and where two or more adjacent R.sup.8 groups can be taken together to form an optionally substituted saturated, partially unsaturated, or aromatic 5- to 12-membered ring containing 0 to 4 heteroatoms; X.sup. is any anionic metal carbonyl compound; Ring A is an optionally substituted, 5- to 10-membered heteroaryl group; and Ring B is an optionally substituted, 3- to 8-membered saturated or partially unsaturated monocyclic heterocyclic ring having 0-2 heteroatoms in addition to the depicted ring nitrogen atom independently selected from nitrogen, oxygen, or sulfur.

9. The catalyst of claim 8, wherein the one or more cationic functional groups are selected from the group consisting of: ##STR00333##

10. The catalyst of claim 9, wherein the one or more cationic functional groups are selected from the group consisting of: ##STR00334##

11. The catalyst of claim 9, wherein the one or more cationic functional groups are selected from the group consisting of: ##STR00335##

12. The catalyst of claim 9, wherein the one or more cationic functional groups are selected from the group consisting of: ##STR00336##

13. The catalyst of claim 1, wherein the cationic functional moiety comprises a linker selected from the group consisting of: a bond, and moieties comprising 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.

14. The catalyst of claim 13, wherein the cationic functional moiety includes a linker comprising optionally substituted C.sub.2-30 aliphatic group wherein one or more methylene units are optionally and independently replaced by: -Cy-, 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, wherein each -Cy- is independently an optionally substituted 5-8 membered bivalent, saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or an optionally substituted 8-10 membered bivalent saturated, partially unsaturated, or aryl bicyclic ring having 0-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and each R.sup.y is independently H, or an optionally substituted radical selected from the group consisting of C.sub.1-.sub.6 aliphatic, phenyl, a 3-7 membered saturated or partially unsaturated carbocyclic ring, a 3-7 membered saturated or partially unsaturated monocyclic heterocyclic ring having 1-2 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 5-6 membered heteroaryl ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, and 8- to 10-membered aryl.

15. The catalyst of claim 1, wherein the at least one anionic metal carbonyl species comprises a compound of formula: [Q.sub.dM.sub.e(CO).sub.w].sup.y, where Q is any ligand and need not be present, M is a metal atom, d is an integer between 0 and 8 inclusive, e is an integer between 1 and 6 inclusive, w is a number such as to provide the stable anionic metal carbonyl complex, and x is the charge of the anionic metal carbonyl compound.

16. The catalyst of claim 15, wherein the anionic metal carbonyl species is selected from the group consisting of: monoanionic carbonyl complexes of metals from groups 5, 7 or 9 of the periodic table, and dianionic carbonyl complexes of metals from groups 4 or 8 of the periodic table.

17. The catalyst of claim 15, wherein the wherein the anionic metal species is selected from the group consisting of: [Co(CO).sub.4].sup., [Ti(CO).sub.6].sup.2, [V(CO).sub.6].sup., [Rh(CO).sub.4].sup., [Fe(CO).sub.4].sup.2, [Ru(CO).sub.4].sup.2, [Os(CO).sub.4].sup.2, [Cr.sub.2(CO).sub.10].sup.2, [Fe.sub.2(CO).sub.8].sup.2, [Tc(CO).sub.5].sup., [Re(CO).sub.5].sup., and [Mn(CO).sub.5].sup..

18. The catalyst of claim 1, wherein the anionic carbonyl species comprise [Co(CO).sub.4].sup..

19. The catalyst of claim 1, wherein the ligand to which at least one cationic functional moiety is covalently tethered and which is coordinated to one or two metal atoms the catalyst has a structure selected from the group consisting of: ##STR00337## where, each represents a cationic functional moiety, where is a bond or a linker moiety, Z is a cationic functional group, and b is an integer from 1 to 4 representing the number of cationic functional groups present on the cationic functional moiety; M is the metal atom; represents is an optionally substituted moiety linking the two nitrogen atoms of the diamine portion of the salen ligand, where is selected from the group consisting of a C.sub.3-C.sub.14 carbocycle, a C.sub.6-C.sub.10 aryl group, a C.sub.3-C.sub.14 heterocycle, and a C.sub.5-C.sub.10 heteroaryl group; 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; R.sup.d at each occurrence is independently a cationic functional moiety (), hydrogen, halogen, OR.sup.4, NR.sub.2.sup.y, SR, CN, NO.sub.2, SO.sub.2R.sup.y, SOR.sup.y, SO.sub.2NR.sub.2.sup.y; CNO, NRSO.sub.2R.sup.y, NCO, N.sub.3, SiR.sub.3; or an optionally substituted group selected from the group consisting of C.sub.1-20 aliphatic; C.sub.1-20heteroaliphatic having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 6- to 10-membered aryl; 5- to 10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and 4- to 7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur, where two or more R.sup.d groups may be taken together to form one or more optionally substituted rings, where each R.sup.y is independently hydrogen, an optionally substituted group selected the group consisting of acyl; carbamoyl, arylalkyl; 6- to 10-membered aryl; C.sub.1-12 aliphatic; C.sub.1-12 heteroaliphatic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 5- to 10-membered heteroaryl having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 4- to 7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; an oxygen protecting group; and a nitrogen protecting group; two R.sup.y on the same nitrogen atom are taken with the nitrogen atom to form an optionally substituted 4- to 7-membered heterocyclic ring having 0-2 additional heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; and each R.sup.4 a hydroxyl protecting group or R.sup.y; R.sup.1 R.sup.2, R.sup.3, and R.sup.4, are independently at each occurrence selected from the group consisting of: hydrogen, halogen, NO.sub.2, CN, SR.sup.y, S(O)R.sup.y, S(O).sub.2R.sup.y, NR.sup.yC(O)R.sup.y, OC(O)R.sup.y, CO.sub.2R.sup.y, NCO, N.sub.3, OR.sup.4, 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; SiR.sub.3; or an optionally substituted group selected from the group consisting of C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 6- to 10-membered aryl; 5- to 10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and 4- to 7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and 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, where each R.sup.y is independently an optionally substituted radical selected from the group consisting of C.sub.1-.sub.6 aliphatic, phenyl, a 3-7 membered saturated or partially unsaturated carbocyclic ring, a 3-7 membered saturated or partially unsaturated monocyclic heterocyclic ring having 1-2 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 5-6 membered heteroaryl ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, and 8- to 10-membered aryl; and a is an integer from 0 to 4 inclusive.

20. The catalyst of claim 1, wherein ligand to which at least one cationic functional moiety is covalently tethered and which is coordinated to one or two metal atoms the catalyst has a structure selected from the group consisting of: ##STR00338## ##STR00339## ##STR00340## where, each represents a cationic functional moiety, where is a bond or a linker moiety, Z is a cationic functional group, and b is an integer from 1 to 4 representing the number of cationic functional groups present on the cationic functional moiety; M is the metal atom; R.sup.d at each occurrence is independently a cationic functional moiety (), hydrogen, halogen, OR.sup.4, NR.sub.2.sup.y, SR, CN, NO.sub.2, SO.sub.2R.sup.y, SOR.sup.y, SO.sub.2NR.sub.2.sup.y; CNO, NRSO.sub.2R.sup.y, NCO, N.sub.3, SiR.sub.3; or an optionally substituted group selected from the group consisting of C.sub.1-20 aliphatic; C.sub.1-20heteroaliphatic having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 6- to 10-membered aryl; 5- to 10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and 4- to 7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur, where two or more R.sup.d groups may be taken together to form one or more optionally substituted rings, where each R.sup.y is independently hydrogen, an optionally substituted group selected the group consisting of acyl; carbamoyl, arylalkyl; 6- to 10-membered aryl; C.sub.1-12 aliphatic; C.sub.1-12 heteroaliphatic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 5- to 10-membered heteroaryl having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 4- to 7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; an oxygen protecting group; and a nitrogen protecting group; two R.sup.y on the same nitrogen atom are taken with the nitrogen atom to form an optionally substituted 4- to 7-membered heterocyclic ring having 0-2 additional heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; and each R.sup.4 a hydroxyl protecting group or R.sup.y; each So is optionally present, and if present is a neutral two electron donor; and a is an integer from 0 to 4 inclusive.

21. A catalyst for the carbonylation of heterocycles comprising a compound selected from Catalyst Table 1, wherein M, is selected from the group consisting of: ##STR00341##

22. A catalyst for the carbonylation of heterocycles comprising a compound selected from Catalyst Table 2, wherein M, is selected from the group consisting of: ##STR00342##

23. A method comprising the step of contacting ethylene oxide with carbon monoxide in the presence of a catalyst of claim 1, to provide a product selected from the group consisting of beta propiolactone, succinic anhydride, polypropiolactone, and a mixture of any two or more of these.

24. The method of claim 23, wherein the product consists substantially of beta propiolactone.

25. The method claim 23, wherein the product consists substantially of polypropiolactone.

26. The catalyst of claim 8, wherein the cationic functional moiety comprises a linker selected from the group consisting of: ##STR00343## ##STR00344## wherein each s is independently 0-6, t is 0-4, * represents the site of attachment to a ligand, and each # represents a site of attachment of a cationic functional group.

Description

DETAILED DESCRIPTION OF CERTAIN EMBODIMENTS

[0071] The present invention encompasses catalysts for the carbonylation of epoxides, aziridines, thiiranes, oxetanes, lactones, lactams and analogous compounds. According to one aspect, the present invention provides carbonylation catalysts comprising a metal complex with one or more cationic functional moieties covalently tethered to a ligand that is coordinated to a metal center of the complex and comprising one or more anionic metal carbonyl compounds. The metal complex contains one or more ligands, one or two metal atoms coordinated to the ligand or ligands, and one or more cationic functional moieties covalently tethered to the ligand. Each cationic functional moiety comprises a linker moiety and one or more cationic functional groups. In certain embodiments, at least one cationic functional group acts as a counterion for the anionic metal carbonyl compound.

[0072] In certain embodiments, provided carbonlyation catalysts of the present invention include a cationic metal complex and at least one anionic metal carbonyl compound balancing the charge of the metal complex. In certain embodiments, there are 1 to 17 such anionic metal carbonyls balancing the charge of the metal complex. In certain embodiments, there are 1 to 9 such anionic metal carbonyls balancing the charge of the metal complex. In certain embodiments, there are 1 to 5 such anionic metal carbonyls balancing the charge of the metal complex. In certain embodiments, there are 1 to 3 such anionic metal carbonyls balancing the charge of the metal complex.

[0073] In certain embodiments, the metal complex has the formula [(L.sup.c).sub.aM.sub.b(L.sup.n).sub.c].sup.2+, where: [0074] L.sup.c is a ligand that includes at least one cationic functional moiety where, when two or more L.sup.c arc present, each may be the same or different; [0075] M is a metal atom where, when two M are present, each may be the same or different; [0076] L.sup.n is optionally present, and if present, is a ligand that does not include a cationic moiety where, when two or more L.sup.n are present, each may be the same or different; [0077] a is an integer from 1 to 4 inclusive; [0078] b is an integer from 1 to 2 inclusive; [0079] c is an integer from 0 to 6 inclusive; and [0080] z is an integer greater than 0 that represents the cationic charge on the metal complex.

[0081] In certain embodiments, provided metal complexes conform to structure I:

##STR00007##

wherein: [0082] is a multidentate ligand; [0083] M is a metal atom coordinated to the multidentate ligand; [0084] a is the charge of the metal atom and ranges from 0 to 2; and [0085] represents a cationic functional moiety, [0086] where is a linker moiety covalently coupled to the multidentate ligand; [0087] Z.sup.+ is a cationic functional group covalently coupled to the linker moiety; and [0088] b is the number of cationic functional groups coupled to the linker moiety and is an integer between 1 and 4 inclusive;

[0089] In certain embodiments, provided metal complexes conform to structure II:

##STR00008## [0090] Where each of and a is as defined above (each a may be the same or different), and [0091] M.sup.1 is a first metal atom; [0092] M.sup.2 is a second metal atom; [0093] comprises a multidentate ligand system capable of coordinating both metal atoms.

[0094] For sake of clarity, and to avoid confusion between the net and total charge of the metal atoms in complexes I and II and other structures herein, the charge (a.sup.+) shown on the metal atom in complexes I and II above represents the net charge on the metal atom after it has satisfied any anionic sites of the multidentate ligand. For example, if a metal atom in a complex of formula I were Cr(III), and the ligand were porphyrin (a tetradentate ligand with a charge of 2), then the chromium atom would have a net change of +1, and a would be 1.

[0095] Before more fully describing the inventive catalysts, the following section provides a more detailed understanding of what the tethered cationic functional moieties are.

I. Cationic Functional Moieties

[0096] As described above, inventive metal complexes of the present invention include one or more cationic functional moieties. Each cationic functional moiety denoted generically herein as comprises a linker coupled to at least one cationic functional group Z, where b denotes the number of cationic functional groups present on a single linker moiety. Thus, a single cationic functional moiety may contain two or more cationic functional groups.

[0097] In some embodiments, there may be one or more cationic functional moieties tethered to a given metal complex; each cationic functional moiety may itself contain more than one cationic functional group Z. In certain embodiments, each cationic functional moiety contains only one cationic functional group (i.e. b=1). In some embodiments, each cationic functional moiety contains more than one cationic functional groups (i.e. b>1). In certain embodiments, an cationic functional moiety contains two cationic functional groups (i.e. b=2). In certain embodiments, an cationic functional moiety contains three cationic functional groups (i.e. b=3). In certain embodiments, an cationic functional moiety contains four cationic functional groups (i.e. b=4). In certain embodiments where more than one cationic functional group is present on an cationic functional moiety, the cationic functional groups are the same. In some embodiments where more than one cationic functional group is present on an cationic functional moiety, two or more of the cationic functional groups are different.

[0098] Ia. Linkers

[0099] In certain embodiments, a linker may comprise a bond. In this case, the cationic functional group Z is bonded directly to the ligand. To avoid the need to arbitrarily define where a ligand ends and a tether begins, it is to be understood that if a Z group is bonded directly to an atom that is typically regarded as part of the parent structure of the ligand, then the linker is to be regarded as comprising a bond. In certain embodiments, when comprises a bond, b is 1.

[0100] In certain embodiments, each linker 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.

[0101] In certain embodiments, a linker is an optionally substituted C.sub.2-30 aliphatic group wherein one or more methylene units are optionally and independently replaced by -Cy-, 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, wherein: [0102] each -Cy- is independently an optionally substituted 5-8 membered bivalent, saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or an optionally substituted 8-10 membered bivalent saturated, partially unsaturated, or aryl bicyclic ring having 0-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and [0103] each R.sup.y is independently H, or an optionally substituted radical selected from the group consisting of C.sub.1-.sub.6 aliphatic, phenyl, a 3-7 membered saturated or partially unsaturated carbocyclic ring, a 3-7 membered saturated or partially unsaturated monocyclic heterocyclic ring having 1-2 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 5-6 membered heteroaryl ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, and 8- to 10-membered aryl.

[0104] In certain embodiments, a linker is a C.sub.4-C.sub.12 aliphatic group substituted with one or more moieties selected from the group consisting of halogen, NO.sub.2, CN, SR.sup.y, S(O)R.sup.y, S(O).sub.2R.sup.y, NR.sup.yC(O)R.sup.y, OC(O)R.sup.y, CO.sub.2R.sup.y, NCO, N.sub.3, OR.sup.4, 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 each R.sup.y and R.sup.4 is independently as defined above and described in classes and subclasses herein.

[0105] In certain embodiments, a linker 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).sub.2 wherein R is as defined above. In certain embodiments, a linker consists of a bivalent aliphatic group having 4 to 30 carbons including one or more C.sub.1-4 alkyl substituted carbon atoms. In certain embodiments, a linker moiety consists of a bivalent aliphatic group having 4 to 30 carbons including one or more gem-dimethyl substituted carbon atoms.

[0106] In certain embodiments, a linker 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.

[0107] In some embodiments, a linker moiety is of sufficient length to allow an atom bearing a positive (either wholly or through a resonance structure) within a cationic functional group to be positioned near a metal atom of a metal complex. In certain embodiments, a linker moiety is of sufficient length to allow an atom bearing a positive within a cationic functional group to be positioned within about 6 , within about 5 , within about 4 , within about 3.5 , or within about 3 . In certain embodiments, structural constraints are built into a linker moiety to control the disposition and orientation of one or more cationic 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, steric interactions due to syn-pentane, gauche-butane, and/or allylic strain in a linker moiety, bring about structural constraints that affect the orientation of a linker and one or more cationic groups. In certain embodiments, 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, 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, structural constraints are selected from the group consisting of heteratom-containing functional groups such as sulfoxides, amides, and oximes.

[0108] In certain embodiments, linker moieties are selected from the group consisting of:

##STR00009## ##STR00010##

[0109] wherein each s is independently 0-6, t is 0-4, R.sup.y as defined above and described in classes and subclasses herein, * represents the site of attachment to a ligand , and each # represents a site of attachment of a cationic functional group.

[0110] 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.

[0111] In some embodiments, t is 1. In some embodiments, t is 2. In some embodiments, t is 3. In some embodiments, t is 4.

[0112] In certain embodiments, there is at least one cationic functional moiety tethered to the multidentate ligand. In certain embodiments, there are 1 to 8 such cationic functional moieties tethered to the multidentate ligand. In certain embodiments, there are 1 to 4 such cationic functional moieties tethered to the multidentate ligand. In certain embodiments, there are 1 to 2 such cationic functional moieties tethered to the multidentate ligand.

Ib. Cationic Functional Groups

[0113] In certain embodiments, one or more tethered cationic groups (Z.sup.+) comprise organic cations. In certain embodiments, one or more tethered cationic groups (Z.sup.+) comprises an onium group. In certain embodiments, such onium groups include one or more nitrogen and/or phosphorous atoms.

[0114] In certain embodiments, one or more tethered cationic groups (Z.sup.+) on provided metal complexes (i.e. complexes of formulae I or II or any of the embodiments, classes or subclasses thereof described herein) is selected from a structure in Table Z-2:

TABLE-US-00001 TABLE Z-2 [00011] [00012] [00013] [00014] [00015] [00016] [00017] [00018] [00019] [00020] [00021] [00022] [00023] [00024] [00025] [00026] [00027] [00028] [00029] [00030] [00031] [00032] [00033] [00034] [00035] [00036] [00037] [00038] [00039] [00040] [00041] or a combination of two or more of these,
wherein: [0115] each 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; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle; a 7- to 14-membered saturated or partially unsaturated polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; an 8- to 14-membered polycyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated monocyclic heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 14-membered saturated or partially unsaturated polycyclic heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; phenyl; or an 8- to 14-membered polycyclic aryl ring; wherein R.sup.1 and R.sup.2 can be taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more additional heteroatoms; [0116] each 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; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle; a 7- to 14-membered saturated or partially unsaturated polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; an 8- to 14-membered polycyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated monocyclic heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 14-membered saturated or partially unsaturated polycyclic heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; phenyl; or an 8- to 14-membered polycyclic aryl ring; wherein an R.sup.3 group can be taken with an R.sup.1 or R.sup.2 group to form one or more optionally substituted rings; and [0117] R.sup.5 is R.sup.2 or hydroxyl; wherein R.sup.1 and R.sup.5 can be taken together with intervening atoms to form one or more optionally substituted carbocyclic, heterocyclic, aryl, or heteroaryl rings; [0118] each R.sup.6 and R.sup.7 is independently hydrogen or an optionally substituted radical selected from the group consisting of C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle; a 7- to 14-membered saturated or partially unsaturated polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; an 8- to 14-membered polycyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated monocyclic heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 14-membered saturated or partially unsaturated polycyclic heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; phenyl; or an 8- to 14-membered polycyclic aryl ring; wherein R.sup.6 and R.sup.7 can be taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more heteroatoms, and an R.sup.6 and R.sup.7 group can be taken with an R.sup.1 or R.sup.2 group to form one or more optionally substituted rings; [0119] each occurrance of R.sup.8 is independently selected from the group consisting of: halogen, NO.sub.2, CN, SR.sup.y, S(O)R.sup.y, S(O).sub.2R.sup.y, NR.sup.yC(O)R.sup.y, OC(O)R.sup.y, CO.sub.2R.sup.y, NCO, 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; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle; a 7- to 14-membered saturated or partially unsaturated polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; an 8- to 14-membered polycyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated monocyclic heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 14-membered saturated or partially unsaturated polycyclic heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; phenyl; or an 8- to 14-membered polycyclic aryl ring; wherein each R.sup.y is independently as defined above and described in classes and subclasses herein, and where two or more adjacent R.sup.8 groups can be taken together to form an optionally substituted saturated, partially unsaturated, or aromatic 5- to 12-membered ring containing 0 to 4 heteroatoms; [0120] X.sup. is any anionic metal carbonyl compound; [0121] Ring A is an optionally substituted, 5- to 10-membered heteroaryl group; and [0122] Ring B is an optionally substituted, 3- to 8-membered saturated or partially unsaturated monocyclic heterocyclic ring having 0-2 heteroatoms in addition to the depicted ring nitrogen atom independently selected from nitrogen, oxygen, or sulfur.

[0123] In certain embodiments, each R.sup.1 group is the same. In other embodiments, R.sup.1 groups are different. 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 a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle; a 7- to 14-membered saturated or partially unsaturated polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; an 8- to 14-membered polycyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated monocyclic heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 14-membered saturated or partially unsaturated polycyclic heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; phenyl; or an 8- to 14-membered polycyclic aryl ring.

[0124] In certain embodiments, R.sup.1 is an optionally substituted radical selected from the group consisting of C.sub.1-12 aliphatic and C.sub.1-12 heteroaliphatic. In some embodiments, R.sup.1 is optionally substituted C.sub.1-20 aliphatic. In some embodiments, R.sup.1 is optionally substituted C.sub.1-12 aliphatic. In some embodiments, R.sup.1 is optionally substituted C.sub.1-6 aliphatic. In some embodiments, R.sup.1 is optionally substituted C.sub.1-20 heteroaliphatic. In some embodiments, R.sup.1 is optionally substituted C.sub.1-12 heteroaliphatic. In some embodiments, R.sup.1 is optionally substituted phenyl. In some embodiments, R.sup.1 is optionally substituted 8- to 10-membered aryl. In some embodiments, R.sup.1 is an optionally substituted 5- to 6-membered heteroaryl group. In some embodiments, R.sup.1 is an optionally substituted 8- to 14-membered polycyclic heteroaryl group. In some embodiments, R.sup.1 is optionally substituted 3- to 8-membered heterocyclic.

[0125] In certain embodiments, each R.sup.1 is independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, optionally substituted phenyl, or optionally substituted benzyl. 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 neopentyl. In some embodiments, R.sup.1 is perfluoro. In some embodiments, R.sup.1 is CF.sub.2CF.sub.3. In some embodiments, R.sup.1 is phenyl. In some embodiments, R.sup.1 is benzyl.

[0126] In certain embodiments, each R.sup.2 group is the same. In other embodiments, R.sup.2 groups are different. In certain embodiments, R.sup.2 is hydrogen. In some embodiments, R.sup.2 is an optionally substituted radical selected from the group consisting of C.sub.1-20 aliphatic; C.sub.1-2o heteroaliphatic, 5- to 14-membered heteroaryl, phenyl, 8- to 10-membered aryl and 3- to 7-membered heterocyclic. In some embodiments, R.sup.2 is an optionally substituted radical selected from the group consisting of a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle; a 7- to 14-membered saturated or partially unsaturated polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; an 8- to 14-membered polycyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated monocyclic heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 14-membered saturated or partially unsaturated polycyclic heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; phenyl; or an 8- to 14-membered polycyclic aryl ring.

[0127] In certain embodiments, R.sup.2 is an optionally substituted radical selected from the group consisting of C.sub.1-12 aliphatic and C.sub.1-12 heteroaliphatic. In some embodiments, R.sup.2 is optionally substituted C.sub.1-20 aliphatic. In some embodiments, R.sup.2 is optionally substituted C.sub.1-12 aliphatic. In some embodiments, R.sup.2 is optionally substituted C.sub.1-6 aliphatic. In some embodiments, R.sup.2 is optionally substituted C.sub.1-20 heteroaliphatic. In some embodiments, R.sup.2 is optionally substituted C.sub.1-12 heteroaliphatic. In some embodiments, R.sup.2 is optionally substituted phenyl. In some embodiments, R.sup.2 is optionally substituted 8- to 10-membered aryl. In some embodiments, R.sup.2 is an optionally substituted 5- to 6-membered heteroaryl group. In some embodiments, R.sup.2 is an optionally substituted 8- to 14-membered polycyclic heteroaryl group. In some embodiments, R.sup.2 is optionally substituted 3- to 8-membered heterocyclic.

[0128] In certain embodiments, each R.sup.2 is independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, optionally substituted phenyl, or optionally substituted benzyl. In certain embodiments, R.sup.2 is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl or benzyl. In some embodiments, R.sup.2 is butyl. In some embodiments, R.sup.2 is isopropyl. In some embodiments, R.sup.2 is neopentyl. In some embodiments, R.sup.2 is perfluoro. In some embodiments, R.sup.2 is CF.sub.2CF.sub.3. In some embodiments, R.sup.2 is phenyl. In some embodiments, R.sup.2 is benzyl.

[0129] In certain embodiments, each R.sup.1 and R.sup.2 are hydrogen. In some embodiments, each R.sup.1 is hydrogen each and each R.sup.2 is other than hydrogen. In some embodiments, each R.sup.2 is hydrogen each and each R.sup.1 is other than hydrogen.

[0130] 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 each 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.

[0131] In some embodiments, R.sup.1 and R.sup.2 are taken together with intervening atoms to form one or more optionally substituted carbocyclic, heterocyclic, aryl, or heteroaryl rings. In certain embodiments, R.sup.1 and R.sup.2 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, wherein R.sup.y is as defined above. 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.

[0132] In certain embodiments, R.sup.3 is H. In certain embodiments, R.sup.3 is optionally C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic, 5- to 14-membered heteroaryl, phenyl, 8- to 10-membered aryl or 3- to 7-membered heterocyclic. In some embodiments, R.sup.3 is an optionally substituted radical selected from the group consisting of a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle; a 7- to 14-membered saturated or partially unsaturated polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; an 8- to 14-membered polycyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated monocyclic heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 14-membered saturated or partially unsaturated polycyclic heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; phenyl; or an 8- to 14-membered polycyclic aryl ring. In certain embodiments, R.sup.3 is optionally substituted C.sub.1-12 aliphatic. In some embodiments, R.sup.3 is optionally substituted C.sub.1-6 aliphatic. In certain embodiments, R.sup.3 is optionally substituted phenyl.

[0133] In certain embodiments, R.sup.3 is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl or benzyl. In some embodiments, R.sup.3 is butyl. In some embodiments, R.sup.3 is isopropyl. In some embodiments, R.sup.3 is perfluoro. In some embodiments, R.sup.3 is CF.sub.2CF.sub.3.

[0134] In some embodiments, one or more R.sup.1 or R.sup.2 groups are taken together with R.sup.3 and intervening atoms to form an optionally substituted heterocyclic or heteroaryl ring. In certain embodiments, R.sup.1 and R.sup.3 are taken together to form an optionally substituted 5- or 6-membered ring. In some embodiments, R.sup.2 and R.sup.3 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.3 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.3 are partially unsaturated or aromatic.

[0135] In some embodiments, a cationic functional group is a quaternary ammonium agroup:

##STR00042##

where each of R.sup.1, R.sup.2, and R.sup.3 is as defined above and described in classes and subclasses herein. In certain embodiments, R.sup.1, R.sup.2, and R.sup.3 are all methyl. In certain embodiments, R.sup.1, R.sup.2, and R.sup.3 are all ethyl. In certain embodiments, R.sup.1, R.sup.2, and R.sup.3 are all n-butyl. In some embodiments, R.sup.3 is hydroxyl, thereby forming a substituted hydroxylamine or N-oxide.

[0136] In certain embodiments, a cationic functional group is a protonated amine:

##STR00043##

where each of R.sup.1 and R.sup.2 is as defined above and described in classes and subclasses herein.

[0137] In specific embodiments, a protonated amine cationic functional group is selected from the group consisting of:

##STR00044## ##STR00045##

[0138] In certain embodiments, a cationic functional group is a guanidinium group:

##STR00046##

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

[0139] In some embodiments, any two or more R.sup.1 or R.sup.2 groups are taken together with intervening atoms to form one or more optionally substituted carbocyclic, heterocyclic, aryl, or heteroaryl rings. In certain embodiments, R.sup.1 and R.sup.2 groups are taken together to form an optionally substituted 5- or 6-membered ring. In some embodiments, three or more R.sup.1 and/or R.sup.2 groups are taken together to form an optionally substituted fused ring system.

[0140] In certain embodiments, a R.sup.1 and R.sup.2 group are taken together with intervening atoms to form a compound selected from:

##STR00047##

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

[0141] In certain embodiments, two or more R.sup.1 and R.sup.2 groups are taken together with intervening atoms to form a compound selected from:

##STR00048##

wherein each R.sup.1 and R.sup.2 is independently as defined above and described in classes and subclasses herein, and Ring G is an optionally substituted 5- to 8-membered saturated or partially unsaturated heterocyclic ring.

[0142] It will be appreciated that when a guanidinium cation is depicted as

##STR00049##

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

##STR00050##

[0143] In specific embodiments, a guanidinium cationic functional group is selected from the group consisting of:

##STR00051##

[0144] In certain embodiments, a guanidinium cationic functional group is selected from the group consisting of:

##STR00052## [0145] where R.sup.a is selected from the group consisting of H, optionally substituted C.sub.1-12 aliphatic, and optionally substituted aryl.

[0146] In some embodiments, a cationic functional group is a phosphonium group

##STR00053##

In certain embodiments, R.sup.1, R.sup.2, and R.sup.3 are independently selected from the group consisting of optionally substituted C.sub.1-C.sub.12 aliphatic, optionally substituted C.sub.6-C.sub.10 aryl, and optionally substituted C.sub.1-C.sub.10 heterocyclic. In certain embodiments, R.sup.1, R.sup.2, and R.sup.3 are phenyl. In certain embodiments, R.sup.1, R.sup.2, and R.sup.3 are n-butyl. In certain embodiments, R.sup.1, R.sup.2, and R.sup.3 are methyl.

[0147] In some embodiments, the cationic functional group is an arsonium group.

##STR00054##

In some embodiments, each occurrence of R.sup.1, R.sup.2, and R.sup.3 is independently hydrogen or optionally substituted C.sub.1-20 aliphatic. In some embodiments, each occurrence of R.sup.1, R.sup.2, and R.sup.3 is independently hydrogen or optionally substituted C.sub.1-20 heteroaliphatic having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur. In some embodiments, each occurrence of R.sup.1, R.sup.2, and R.sup.3 is independently hydrogen or optionally substituted 6- to 10-membered aryl. In some embodiments, each occurrence of R.sup.1, R.sup.2, and R.sup.3 is independently hydrogen or optionally substituted 5- to 10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur. In some embodiments, each occurrence of R.sup.1, R.sup.2, and R.sup.3 is independently hydrogen or optionally substituted 4- to 7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur. In some embodiments, R.sup.1 and R.sup.2 are taken together with their 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 C.sub.5-C.sub.10 heteroaryl.

[0148] In specific embodiments, an arsonium cationic functional group is selected from the group consisting of:

##STR00055##

[0149] In some embodiments, a cationic functional group is a sulfonium group:

##STR00056##

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

[0150] In some embodiments, a cationic 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.

[0151] In some embodiments, a nitrogen-containing heterocycle includes a quaternized nitrogen atom. In certain embodiments, a nitrogen-containing heterocycle includes an iminium moiety such as

##STR00057##

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.

[0152] 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.

[0153] In some embodiments, a cationic functional group is

##STR00058##

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.

[0154] In some embodiments, when Z is

##STR00059##

ring A is other than an imidazole, an oxazolc, or a thiazolc.

[0155] In specific embodiments, a nitrogen-containing heterocyclic cationic functional group is selected from the group consisting of:

##STR00060## ##STR00061##

[0156] In certain embodiments, Ring B is a 5-membered saturated or partially unsaturated monocyclic heterocyclic ring. In certain embodiments, Ring B is a 6-membered saturated or partially unsaturated heterocycle. In certain embodiments, Ring B is a 7-membered saturated or partially unsaturated heterocycle. In certain embodiments, Ring B is tetrahydrofuranyl, tetrahydrothienyl, pyrrolidinyl, pyrrolidonyl, piperidinyl, pyrrolinyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, decahydroquinolinyl, oxazolidinyl, piperazinyl, dioxanyl, dioxolanyl, diazepinyl, oxazepinyl, thiazepinyl, morpholinyl, and quinuclidinyl. In some embodiments, Ring B is piperidinyl.

[0157] In some embodiments, a cationic functional group is an N-linked amidinium group such as:

##STR00062##

where each R.sup.1, R.sup.2, and R.sup.3 is independently as defined above and described in classes and subclasses herein. In certain embodiments, an N-linked amidinium cation comprises a cyclic amidine such as an imidazolium group. In certain embodiments, an N-linked amidinium cation comprises a bicyclic amidinium group. In certain embodiments, such a group comprises:

##STR00063##

[0158] In some embodiments, a cationic functional group is a C-linked amidinium group

##STR00064##

wherein each R.sup.1 and R.sup.2 is independently as defined above and described in classes and subclasses herein.

[0159] In some embodiments, a cationic functional group is

##STR00065##

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

[0160] In some embodiments, a cationic functional group is

##STR00066##

wherein each of R.sup.1, R.sup.2, R.sup.6, and R.sup.7 is as defined above and described in classes and subclasses herein.

[0161] In certain embodiments, R.sup.6 and R.sup.7 are each independently an optionally substituted group selected from the group consisting of C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic; phenyl, and 8-10-membered aryl. In some embodiments, R.sup.6 and R.sup.7 are each independently an optionally substituted C.sub.1-20 aliphatic. In some embodiments, R.sup.6 and R.sup.7 are each independently an optionally substituted C.sub.1-20 heteroaliphatic having. In some embodiments, R.sup.6 and R.sup.7 are each independently an optionally substituted phenyl or 8-10-membered aryl. In some embodiments, R.sup.6 and R.sup.7 are each independently an optionally substituted 5- to 10-membered heteroaryl. In some embodiments, R.sup.6 and R.sup.7 can be taken together with intervening atoms to form one or more rings selected from the group consisting of: optionally substituted C.sub.3-C.sub.14 carbocycle, optionally substituted C.sub.3-C.sub.14 heterocycle, optionally substituted C.sub.6-C.sub.10 aryl, and optionally substituted 5- to 10-membered heteroaryl. In some embodiments, R.sup.6 and R.sup.7 are each independently an optionally substituted C.sub.1-6 aliphatic. In some embodiments, each occurrence of R.sup.6 and R.sup.7 is independently methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, or benzyl. In some embodiments, each occurrence of R.sup.6 and R.sup.7 is independently perfluoro. In some embodiments, each occurrence of R.sup.6 and R.sup.7 is independently CF.sub.2CF.sub.3.

[0162] In some embodiments, a cationic functional group is

##STR00067##

where each of R.sup.1, R.sup.2, and R.sup.3 is as defined above and in the classes and subclasses herein. In certain embodiments, R.sup.1, R.sup.2, and R.sup.3 are each independently selected from the group consisting of optionally substituted C.sub.1-C.sub.12 aliphatic, optionally substituted C.sub.6-C.sub.10 aryl, and optionally substituted C.sub.1-C.sub.10 heterocyclic. In certain embodiments, R.sup.1, R.sup.2, and R.sup.3 are each phenyl.

[0163] In some embodiments, a cationic functional group is

##STR00068##

wherein each R.sup.1 and R.sup.2 is independently as defined above and described in classes and subclasses herein.

[0164] In some embodiments, a cationic functional group is

##STR00069##

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

[0165] In some embodiments, a cationic functional group is

##STR00070##

wherein each R.sup.1 and R.sup.2 is independently as defined above and described in classes and subclasses herein.

[0166] In some embodiments, a cationic functional group is

##STR00071##

wherein each R.sup.1 and R.sup.2 is independently as defined above and described in classes and subclasses herein.

[0167] In some embodiments, a cationic functional group is

##STR00072##

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

[0168] In some embodiments, a cationic functional group is

##STR00073##

wherein each R.sup.1 and R.sup.2 is independently as defined above and described in classes and subclasses herein.

II. Metal Complexes

[0169] As described above, the catalysts of the present invention comprise one or more ligands. While many examples and embodiments herein are focused on the presence of a single multidentate ligand, this is not a limiting principle of the present invention and it is to be understood that two or more mono- or multidentate ligands may also be used, when two or more ligands are used, they need not all be substituted with tethered cationic functional moieties, only one ligand may be so substituted, or more than one may be substituted with one or more cationic functional moieties.

[0170] Suitable multidentate ligands include, but are not limited to: porphyrin derivatives 1, salen derivatives 2, dibenzotetramethyltetraaza[14]annulene (tmtaa) derivatives 3, phthalocyaninate derivatives 4, derivatives of the Trost ligand 5, and tetraphenylporphyrin derivatives 6. In certain embodiments, the multidentate ligand is a salen derivative. In other embodiments, the multidentate ligand is a tetraphenylporphyrin derivative.

##STR00074## ##STR00075##

[0171] where each of R.sup.c, R.sup.d, R.sup.a, R.sup.1a, R.sup.2a, R.sup.3a, R.sup.1a, R.sup.2a, R.sup.3a, and m, is as defined and described in the classes and subclasses herein.

[0172] In certain embodiments, catalysts of the present invention comprise metal-porphinato complexes. In certain embodiments, the moiety has the structure:

##STR00076## [0173] where each of M and a is as defined above and described in the classes and subclasses herein, and [0174] R.sup.d at each occurrence is independently a cationic functional moiety (), hydrogen, halogen, OR.sup.4, NR.sub.2.sup.y, SR, CN, NO.sub.2, SO.sub.2R.sup.y, SOR.sup.y, SO.sub.2NR.sub.2.sup.y; CNO, NRSO.sub.2R.sup.y, NCO, N.sub.3, SiR.sub.3; or an optionally substituted group selected from the group consisting of C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 6- to 10-membered aryl; 5- to 10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and 4- to 7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur, where two or more R.sup.d groups may be taken together to form one or more optionally substituted rings, where each R.sup.y is independently hydrogen, an optionally substituted group selected the group consisting of acyl; carbamoyl, arylalkyl; 6- to 10-membered aryl; C.sub.1-12 aliphatic; C.sub.1-12 heteroaliphatic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 5- to 10-membered heteroaryl having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 4- to 7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; an oxygen protecting group; and a nitrogen protecting group; two R.sup.y on the same nitrogen atom are taken with the nitrogen atom to form an optionally substituted 4- to 7-membered heterocyclic ring having 0-2 additional heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; and each R.sup.4 a hydroxyl protecting group or R.sup.y;

[0175] In certain embodiments, the multidentate ligand is a porphyrin moiety. Examples include, but are not limited to:

##STR00077## ##STR00078##

[0176] where M, a and R.sup.d are as defined above and in the classes and subclasses herein,

[0177] and So, is an optionally present coordinated solvent molecule, such as an ether, epoxide, DMSO, amine or other Lewis basic moiety.

[0178] In certain embodiments, the moiety has the structure:

##STR00079##

[0179] where M, a and R.sup.d are as defined above and in the classes and subclasses herein.

[0180] In certain embodiments, the multidentate ligand is an optionally substituted tetraphenyl porphyrin. Suitable examples include, but are not limited to:

##STR00080## ##STR00081## ##STR00082##

where M, a, R, So and are as defined above and described in the classes and subclasses herein.

[0181] In certain embodiments, the moiety has the structure:

##STR00083##

where M, a and R.sup.d are as defined above and in the classes and subclasses herein.

[0182] In certain embodiments, catalysts of the present invention comprise metallo salenate complexes. In certain embodiments, the moiety has the structure:

##STR00084##

wherein: [0183] M, and a are as defined above and in the classes and subclasses herein. [0184] R.sup.1a, R.sup.1a, R.sup.2a, R.sup.2a, R.sup.3a, and R.sup.3a are independently a cationic functional moiety (), hydrogen, halogen, OR.sup.4, NR.sub.2.sup.y, SR, CN, NO.sub.2, SO.sub.2R.sup.y, SOR, SO.sub.2NR.sub.2.sup.y; CNO, NRSO.sub.2R.sup.y, NCO, N.sub.3, SiR.sub.3; or an optionally substituted group selected from the group consisting of C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 6- to 10-membered aryl; 5- to 10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and 4- to 7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; wherein each R, R.sup.4, and R.sup.y is independently as defined above and described in classes and subclasses herein, [0185] 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 groups; and [0186] R.sup.4a is selected from the group consisting of:

##STR00085## [0187] where [0188] R.sup.c at each occurrence is independently a cationic functional moiety (), hydrogen, halogen, OR, NR.sub.2.sup.y, SR.sup.y, CN, NO.sub.2, SO.sub.2R.sup.y, SOR.sup.y, SO.sub.2NR.sub.2.sup.y; CNO, NRSO.sub.2R.sup.y, NCO, N.sub.3, SiR.sub.3; or an optionally substituted group selected from the group consisting of C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 6- to 10-membered aryl; 5- to 10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and 4- to 7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; [0189] where: [0190] 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 rings; [0191] when two R.sup.c 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; [0192] Y is a divalent linker selected from the group consisting of: NR.sup.y, N(R)C(O), C(O)NR.sup.y, O, C(O), OC(O), C(O)O, S, SO, SO.sub.2, C(S), C(NR.sup.y), 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; [0193] m is 0 or an integer from 1 to 4, inclusive; [0194] q is 0 or an integer from 1 to 4, inclusive; and [0195] x is 0, 1, or 2.

[0196] In certain embodiments, a provided metal complex comprises at least one cationic functional moiety tethered to a carbon atom of only one phenyl ring of the salicylaldehyde-derived portion of a salen ligand, as shown in formula Ia:

##STR00086## [0197] wherein each of , M, R.sup.d, and a, is as defined above and in the classes and subclasses herein, [0198] represents is an optionally substituted moiety linking the two nitrogen atoms of the diamine portion of the salen ligand, where is selected from the group consisting of a C.sub.3-C.sub.14 carbocycle, a C.sub.6-C.sub.10 aryl group, a C.sub.3-C.sub.14 heterocycle, and a C.sub.5-C.sub.10 heteroaryl group; 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.

[0199] In certain embodiments, provided metal complexes of the present invention feature cationic functional moieties tethered to only one salicylaldehyde-derived portion of the salen ligand, while in other embodiments both salicylaldehyde-derived portions of the salen ligand bear one or more cationic functional moieties as in IIa:

##STR00087## [0200] where each of M, a, So, R.sup.d, , and are as defined above and in the classes and subclasses herein.

[0201] In certain embodiments of metal complexes having formulae Ia or IIa above, at least one of the phenyl rings comprising the salicylaldehyde-derived portion of the metal complex is independently selected from the group consisting of:

##STR00088## ##STR00089## ##STR00090## ##STR00091## ##STR00092## [0202] where represents one or more independently-defined cationic functional moieties which may be bonded to any one or more of the unsubstituted positions of the salicylaldehyde-derived phenyl ring.

[0203] In certain embodiments, there is a cationic functional moiety tethered to the position ortho to the metal-bound oxygen substituent of one or both of the salicylaldehyde-derived phenyl rings of the salen ligand as in formulae IIIa and IIIb:

##STR00093## [0204] where each of M, a, R.sup.d, , and is as defined above, and in the classes and subclasses herein, and [0205] R.sup.2, R.sup.3, and R.sup.4, are independently at each occurrence selected from the group consisting of: hydrogen, halogen, NO.sub.2, CN, SR.sup.y, S(O)R.sup.y, S(O).sub.2R.sup.y, NR.sup.yC(O)R.sup.y, OC(O)R.sup.y, CO.sub.2R.sup.y, NCO, N.sub.3, OR.sup.y, OC(O)N(R.sup.y).sub.2, N(R.sup.y).sub.2, NR.sup.yC(O)R.sup.y, NR.sup.yC(O)OR.sup.y; SiR.sub.3; or an optionally substituted group selected from the group consisting of C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 6- to 10-membered aryl; 5- to 10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and 4- to 7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and 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, where R.sup.y is as defined above

[0206] In certain embodiments of metal complexes having formulae IIIa or IIIb, R.sup.2 and R.sup.4 are each hydrogen, and each R.sup.3 is, independently, H, or optionally substituted C.sub.1-C.sub.20 aliphatic.

[0207] In certain embodiments of metal complexes IIIa and IIIb, at least one of the phenyl rings comprising the salicylaldehyde-derived portion of the metal complex is independently selected from the group consisting of:

##STR00094## ##STR00095##

[0208] In other embodiments, there is a cationic functional moiety tethered to the position para to the phenolic oxygen of one or both of the salicylaldehyde-derived phenyl rings of the salen ligand as in structures IVa and IVb:

##STR00096## [0209] where each R.sup.1 is independently selected from the group consisting of: hydrogen, halogen, NO.sub.2, CN, SR.sup.y, S(O)R.sup.y, S(O).sub.2R.sup.y, NR.sup.yC(O)R.sup.y, OC(O)R.sup.y, CO.sub.2R.sup.y, NCO, N.sub.3, OR.sup.y, OC(O)N(R.sup.y).sub.2, N(R.sup.y).sub.2, NR.sup.yC(O)R.sup.y, NR.sup.yC(O)OR.sup.y; or an optionally substituted group selected from the group consisting of C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 6- to 10-membered aryl; 5- to 10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and 4- to 7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur, where adjacent R.sup.1 and R.sup.2 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,

[0210] In certain embodiments of metal complexes having formulae IVa or IVb, R.sup.2 and R.sup.4 are hydrogen, and each R.sup.1 is, independently, optionally substituted C.sub.1-C.sub.20 aliphatic.

[0211] In certain embodiments of metal complexes IVa and IVb, at least one of the phenyl rings comprising the salicylaldehyde-derived portion of the metal complex is independently selected from the group consisting of:

##STR00097## ##STR00098##

[0212] In still other embodiments, there is a cationic functional moiety tethered to the position para to the imine substituent of one or both of the salicylaldehyde-derived phenyl rings of the salen ligand as in formulae Va or Vb:

##STR00099## [0213] where M, a, R.sup.d, R.sup.1, R.sup.3, R.sup.4, , and are as defined above and in the classes and subclasses herein.

[0214] In certain embodiments of metal complexes having formulae Va or Vb, each R.sup.4 is hydrogen, and each R.sup.1 and R.sup.3 is, independently, hydrogen or optionally substituted C.sub.1-C.sub.20 aliphatic.

[0215] In certain embodiments of metal complexes Va and Vb, at least one of the phenyl rings comprising the salicylaldehyde-derived portion of the metal complex is independently selected from the group consisting of:

##STR00100## ##STR00101## ##STR00102## ##STR00103##

[0216] In still other embodiments, there is a cationic functional moiety tethered to the position para to the imine substituent of one or both of the salicylaldehyde-derived phenyl rings of the salen ligand as in formulae VIa and VIb:

##STR00104## [0217] where M, a, R.sup.d, R.sup.1, R.sup.2, R.sup.3, , and are as defined above and in the classes and subclasses herein.

[0218] In certain embodiments of metal complexes having formulae VIa or VIb, each R.sup.2 is hydrogen, and each R.sup.1 and R.sup.3 is, independently, hydrogen or optionally substituted C.sub.1-C.sub.20 aliphatic.

[0219] In certain embodiments of metal complexes VIa and VIb, at least one of the phenyl rings comprising the salicylaldehyde-derived portion of the metal complex is independently selected from the group consisting of:

##STR00105## ##STR00106## ##STR00107##

[0220] In still other embodiments, there are cationic functional moieties tethered to the positions ortho and para to the phenolic oxygen of one or both of the salicylaldehyde-derived phenyl rings of the salen ligand as in formulae VIIa and VIIb:

##STR00108## [0221] where each of M, a, R.sup.d, R.sup.2, R.sup.4, , and , is as defined above and in the classes and subclasses herein.

[0222] In certain embodiments of compounds having formulae VIIa or VIIb, each R.sup.2 and R.sup.4 is, independently, hydrogen or optionally substituted C.sub.1-C.sub.20 aliphatic.

[0223] In certain embodiments of compounds having formulae VIIa or VIIb, each R.sup.2 and R.sup.4 is hydrogen.

[0224] In still other embodiments, there are cationic functional moieties tethered to the positions ortho and para to the imine substituent of one or both of the salicylaldehyde-derived phenyl rings of the salen ligand as in formulae VIIIa and VIIIb:

##STR00109## [0225] where each of M, a, R.sup.d, R.sup.1, R.sup.3, , and is as defined above and in the classes and subclasses herein.

[0226] In certain embodiments of metal complexes having formulae VIIIa or VIIIb, each R.sup.1 and R.sup.3 is, independently, optionally, hydrogen or substituted C.sub.1-C.sub.20 aliphatic.

[0227] In certain embodiments of the present invention, metal complexes of structures VIIIa or VIIIb above, at least one of the phenyl rings comprising the salicylaldehyde-derived portion of the catalyst is independently selected from the group consisting of:

##STR00110## ##STR00111## ##STR00112## ##STR00113##

[0228] In yet other embodiments, there is a cationic functional moiety tethered to the imine carbon of the salen ligand as in formulae IXa and IXb:

##STR00114## [0229] where M, a, R, R.sup.1, R.sup.2, R.sup.3, R.sup.4, , and are as defined above with the proviso that the atom of the cationic functional moiety attached to the salen ligand is a carbon atom.

[0230] In certain embodiments of compounds having formulae IXa or IXb, each R.sup.2 and R.sup.4 is hydrogen, and each R.sup.1 and R.sup.3 is, independently, hydrogen or optionally substituted C.sub.1-C.sub.20 aliphatic.

[0231] In certain embodiments of the present invention, catalysts of structures IXa or IXb above, at least one of the phenyl rings comprising the salicylaldehyde-derived portion of the metal complex is independently selected from the group consisting of:

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

[0232] 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 metal complex may have a cationic functional moiety attached to different positions on each of the two rings, and such metal complexes are specifically encompassed within the scope of the present invention. Furthermore, cationic functional moieties can be present on multiple parts of the ligand, for instance cationic functional moieties can be present on the diamine bridge and on one or both phenyl rings in the same metal complex.

[0233] In certain embodiments, the salen ligand cores of metal complexes 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 cationic functional moieties as described above.

##STR00118##

[0234] where M, a, R, , and are as defined above and in the classes and subclasses herein.

[0235] In another embodiment, at least one cationic functional moiety is tethered to the diamine-derived portion of the salen ligand, as shown in formula X:

##STR00119## [0236] where M, a, R.sup.d, R.sup.c, , and are as defined above and in the classes and subclasses herein.

[0237] In certain embodiments, salen ligands of formula X are selected from an optionally substituted moiety consisting of:

##STR00120## ##STR00121## [0238] where M, a, R.sup.d, and are as defined above and in the classes and subclasses herein.

[0239] In certain embodiments, the diamine bridge of metal complexes of formula Xa an optionally substituted moiety selected from the group consisting of:

##STR00122## [0240] where each of M, a, and is as defined above and described in the classes and subclasses herein.

[0241] In certain embodiments, catalysts of the present invention comprise metal-tmtaa complexes. In certain embodiments, the moiety has the structure:

##STR00123## [0242] where M, a and R.sup.d are as defined above and in the classes and subclasses herein, and [0243] R.sup.e at each occurrence is independently a cationic functional moiety , 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 group selected from the group consisting of C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 6- to 10-membered aryl; 5- to 10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and 4- to 7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur.

[0244] In certain embodiments, the moiety has the structure:

##STR00124## [0245] where each of M, a, R.sup.c and R.sup.d is as defined above and in the classes and subclasses herein.

[0246] In certain embodiments, at least one activating moiety is tethered to a diamine bridge of a ligand, as shown in formula III-a, III-b, and III-c:

##STR00125## [0247] wherein each of R.sup.c, R.sup.d, R.sup.e, Z, b, M.sup.1, and M.sup.2, is independently as defined above the described in classes and subclasses herein, and [0248] R.sup.12 is optionally present, and if present is selected from the group consisting of: a group; or an optionally substituted radical selected from the group consisting of C.sub.1-20 aliphatic; C.sub.1-20 heteroaliphatic; and phenyl.

[0249] In certain embodiments, at least one activating moiety is tethered to a diamine bridge of a ligand, as shown in formula IV-a, IV-b, and IV-c:

##STR00126## [0250] wherein each of R.sup.c, R.sup.d, R.sup.e, Z, b, M.sup.1, M.sup.2, and R.sup.12 is independently as defined above the described in classes and subclasses herein.

[0251] In certain embodiments, at least one activating moiety is tethered to a cyclic diamine bridge of a ligand, as shown in formula V-a, V-b, and V-c:

##STR00127## [0252] wherein each of R.sup.c, R.sup.d, R.sup.e, Z, b, M.sup.1, M.sup.2, and R.sup.12 is independently as defined above the described in classes and subclasses herein.

[0253] In certain embodiments, at least one activating moiety is tethered to a cyclic diamine bridge of a ligand, as shown in formula VI-a, VI-b, and VI-c:

##STR00128## [0254] wherein each of R.sup.c, R.sup.d, R.sup.e, Z, b, M.sup.1, M.sup.2, and R.sup.12 is independently as defined above the described in classes and subclasses herein.

[0255] In certain embodiments, catalysts of the present invention comprise ligands capable of coordinating two metal atoms.

##STR00129## [0256] wherein each of R.sup.d, R.sup.e, M.sup.1, M.sup.2, and is independently as defined above and described in classes and subclasses herein.

III. Metal Atoms

[0257] In certain embodiments, the metal atom M in any of the metal complexes described above and in the classes, subclasses and tables herein, is selected from the periodic table groups 2-13, inclusive. In certain embodiments, M is a transition metal selected from the periodic table groups 4, 6, 11, 12 and 13. In certain embodiments, M is aluminum, chromium, titanium, indium, gallium, zinc cobalt, or copper. In certain embodiments, M is aluminum. In other embodiments, M is chromium.

[0258] In certain embodiments, M has an oxidation state of +2. In certain embodiments, M is Zn(II), Cu(II), Mn(II), Co(II), Ru(II), Fe(II), Co(II), Rh(II), Ni(II), Pd(II) or Mg(II). In certain embodiments M is Zn(II). In certain embodiments M is Cu(II).

[0259] In certain embodiments, M has an oxidation state of +3. In certain embodiments, M is Al(III), Cr(III), Fe(III), Co(III), Ti(III) In(III), Ga(III) or Mn(III). In certain embodiments M is Al(III). In certain embodiments M is Cr(III).

[0260] In certain embodiments, M has an oxidation state of +4. In certain embodiments, M is Ti(IV) or Cr(IV).

[0261] In certain embodiments, M.sup.1 and M.sup.2 are each independently a metal atom selected from the periodic table groups 2-13, inclusive. In certain embodiments, M is a transition metal selected from the periodic table groups 4, 6, 11, 12 and 13. In certain embodiments, M is aluminum, chromium, titanium, indium, gallium, zinc cobalt, or copper. In certain embodiments, M is aluminum. In other embodiments, M is chromium. In certain embodiments, M.sup.1 and M.sup.2 are the same. In certain embodiments, M.sup.1 and M.sup.2 are the same metal, but have different oxidation states. In certain embodiments, M.sup.1 and M.sup.2 are different metals.

[0262] In certain embodiments, one or more of M.sup.1 and M.sup.2 has an oxidation state of +2. In certain embodiments, M.sup.1 is Zn(II), Cu(II), Mn(II), Co(II), Ru(II), Fe(II), Co(II), Rh(II), Ni(II), Pd(II) or Mg(II). In certain embodiments M.sup.1 is Zn(II). In certain embodiments M.sup.1 is Cu(II). In certain embodiments, M.sup.2 is Zn(II), Cu(II), Mn(II), Co(II), Ru(II), Fe(II), Co(II), Rh(II), Ni(II), Pd(II) or Mg(II). In certain embodiments M.sup.2 is Zn(II). In certain embodiments M.sup.2 is Cu(II).

[0263] In certain embodiments, one or more of M.sup.1 and M.sup.2 has an oxidation state of +3. In certain embodiments, M.sup.1 is Al(III), Cr(III), Fe(III), Co(III), Ti(III) In(III), Ga(III) or Mn(III). In certain embodiments M.sup.1 is Al(III). In certain embodiments M.sup.1 is Cr(III). In certain embodiments, M.sup.2 is Al(III), Cr(III), Fe(III), Co(III), Ti(III) In(III), Ga(III) or Mn(III). In certain embodiments M.sup.2 is Al(III). In certain embodiments M.sup.2 is Cr(III).

[0264] In certain embodiments, one or more of M.sup.1 and M.sup.2 has an oxidation state of +4. In certain embodiments, M.sup.1 is Ti(IV) or Cr(IV). In certain embodiments, M.sup.2 is Ti(IV) or Cr(IV).

[0265] In certain embodiments, one or more neutral two electron donors coordinate to M M.sup.1 or M.sup.2 and fill the coordination valence of the metal atom. In certain embodiments, the neutral two electron donor is a solvent molecule. In certain embodiments, the neutral two electron donor is an ether. In certain embodiments, the neutral two electron donor is tetrahydrofuran, diethyl ether, acetonitrile, carbon disulfide, or pyridine. In certain embodiments, the neutral two electron donor is tetrahydrofuran. In certain embodiments, the neutral two electron donor is an epoxide. In certain embodiments, the neutral two electron donor is an ester or a lactone.

IV. Metal Carbonyl Anions

[0266] In certain embodiments, the anionic metal carbonyl compound has the general formula [Q.sub.dM.sub.e(CO).sub.w].sup.y, where Q is any ligand and need not be present, M is a metal atom, d is an integer between 0 and 8 inclusive, e is an integer between 1 and 6 inclusive, w is a number such as to provide the stable anionic metal carbonyl complex, and x is the charge of the anionic metal carbonyl compound. In certain embodiments, the anionic metal carbonyl has the general formula [QM(CO).sub.w].sup.y, where Q is any ligand and need not be present, M is a metal atom, w is a number such as to provide the stable anionic metal carbonyl, and y is the charge of the anionic metal carbonyl.

[0267] In certain embodiments, the anionic metal carbonyl compounds include monoanionic carbonyl complexes of metals from groups 5, 7 or 9 of the periodic table and dianionic carbonyl complexes of metals from groups 4 or 8 of the periodic table. In some embodiments, the anionic metal carbonyl compound contains cobalt or manganese. In some embodiments, the anionic metal carbonyl compound contains rhodium. Suitable anionic metal carbonyl compounds include, but are not limited to: [Co(CO).sub.4].sup., [Ti(CO).sub.6].sup.2 [V(CO).sub.6].sup. [Rh(CO).sub.4].sup., [Fe(CO).sub.4].sup.2[Ru(CO).sub.4].sup.2, [Os(CO).sub.4].sup.2[Cr.sub.2(CO).sub.10].sup.2[Fe.sub.2(CO).sub.8].sup.2 [Tc(CO).sub.5].sup. [Re(CO).sub.5].sup. and [Mn(CO).sub.5].sup.. In certain embodiments, the anionic metal carbonyl is [Co(CO).sub.4].sup.. In some cases, a mixture of two or more anionic metal carbonyl complexes may be present in the catalyst.

[0268] The term such as to provide a stable anionic metal carbonyl for [Q.sub.dM.sub.e(CO).sub.w].sup.y is used herein to mean that [Q.sub.dM.sub.e(CO).sub.w].sup.y is a species characterizable by analytical means, e.g., NMR, IR, X-ray crystrallography, Raman spectroscopy and/or electron spin resonance (EPR) and isolable in catalyst form as the anion for a metal complex cation or a species formed in situ.

[0269] In certain embodiments, one or two of the CO ligands of any of the metal carbonyl compounds described above is replaced with a ligand Q. In certain embodiments, the ligand Q is present and represents a phosphine ligand. In certain embodiments, Q is present and represents a cyclopentadienyl (cp) ligand.

V. Carbonylation Catalysts

[0270] In certain embodiments, catalysts of the present invention include the combination of: [0271] iv) one or more cationic functional moieties, where each cationic functional moiety comprising comprising the combination of a linker as defined in Section Ia above and 1 to 4 cationic functional groups as defined in Section Ib above; [0272] v) one or more ligands as defined in Section II to which at least one cationic functional moiety is covalently tethered and the ligand(s) is/are coordinated to one or two metal atoms as described in Section III to form a metal complex; and [0273] vi) at least one anionic metal carbonyl species associated with a cation present on the metal complex.

[0274] In certain embodiments, catalysts of the present invention include a complex chosen from Catalyst Table 1:

TABLE-US-00002 CATALYST TABLE 1 [00130] [00131] [00132] [00133] [00134] [00135] [00136] [00137] [00138] [00139] [00140] [00141] [00142] [00143] [00144]

[0275] In certain embodiments, catalysts of the present invention include a complex chosen from Catalyst Table 2:

TABLE-US-00003 CATALYST TABLE 2 [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]

[0276] In certain embodiments, catalysts of the present invention include a complex chosen from Catalyst Table 3:

TABLE-US-00004 CATALYST TABLE 3 [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] [00241] [00242] [00243] [00244] [00245] [00246] [00247] [00248] [00249] [00250] [00251] [00252] [00253] [00254] [00255] [00256] [00257] [00258] [00259] [00260] [00261] [00262] [00263] [00264] [00265] [00266] [00267] [00268] [00269] [00270] [00271] [00272] [00273] [00274] [00275] [00276] [00277] [00278] [00279] [00280] [00281] [00282] [00283] [00284] [00285] [00286] [00287] [00288] [00289] [00290] [00291] [00292] [00293] [00294] [00295] [00296] [00297] [00298] [00299] [00300] [00301] [00302] [00303] [00304] [00305] [00306] [00307] [00308] [00309] [00310] [00311] [00312]

[0277] In certain embodiments, each occurrence of M in any compound of Catalyst Tables 1-3 comprises a moiety:

##STR00313##

[0278] In certain embodiments, each occurrence of M in any compound of Catalyst Tables 1-3 comprises a moiety:

##STR00314##

[0279] In certain embodiments, each occurrence of M in any compound of Catalyst Tables 1-3 comprises a moiety:

##STR00315##

[0280] In certain embodiments, each occurrence of M in any compound of Catalyst Tables 1-3 comprises a moiety:

##STR00316##

[0281] In certain embodiments, the tetracarbonyl cobaltate anions shown associated with any of the compounds in Catalyst Tables 1-3 are replaced by [Rh(CO).sub.4].sup.. In certain embodiments, the tetracarbonyl cobaltate anions shown associated with any of the compounds in Catalyst Tables 1-3 are replaced by [Fe(CO).sub.5].sup.2. In certain embodiments, the tetracarbonyl cobaltate anions shown associated with any of the compounds in Catalyst Tables 1-3 are replaced by [Mn(CO).sub.5].sup..

[0282] In certain embodiments, catalysts of the present invention are selected from the group consisting of:

##STR00317## ##STR00318## ##STR00319## ##STR00320##

VI. Carbonylation Methods

[0283] In another aspect, the present invention provides methods of carbonylating heterocycles using the catalysts disclosed hereinabove. In certain embodiments, the invention encompasses a method comprising the steps: [0284] a) providing a compound having formula:

##STR00321## [0285] wherein: [0286] R.sup.a is hydrogen or an optionally substituted group selected from the group consisting of C.sub.1-30 aliphatic; C.sub.1-30 heteroaliphatic having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 6- to 10-membered aryl; 5- to 10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and 4- to 7-membered heterocyclic having 1-3 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; [0287] each of R.sup.b, R.sup.c, and R.sup.d is independently hydrogen or an optionally substituted group selected from the group consisting of C.sub.1-12 aliphatic; C.sub.1-12heteroaliphatic having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 6- to 10-membered aryl; 5- to 10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and 4- to 7-membered heterocyclic having 1-3 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; [0288] wherein any of (R.sup.b and R.sup.c), (R.sup.c and R.sup.d), and (R.sup.a and R.sup.b) can be taken together with their 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 C.sub.5-C.sub.10 heteroaryl; [0289] X is selected from the group consisting of O, S an NR.sup.c where R.sup.c is selected from the group consisting of hydrogen or an optionally substituted group selected from the group consisting of C.sub.1-30 aliphatic; C.sub.1-30 heteroaliphatic having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 6- to 10-membered aryl; 5- to 10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and 4- to 7-membered heterocyclic having 1-3 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; [0290] n is 0 or 1; and [0291] Y is CO or CH.sub.2; [0292] b) contacting the compound having the formula (1) and carbon monoxide in the presence of any metal complex described above, to provide a product having formula:

##STR00322##

[0293] where R.sup.a, R.sup.b, R.sup.c, R.sup.d, and X, correspond to R.sup.a, R.sup.b, R.sup.c, R.sup.d, and X, in (1) including R.sup.b and R.sup.c forming a ring if that is the case for (1); and in the case where n for (1) is 0, n for (2) is 0 or 1, and in the case where n for (1) is 1, n for (2) is 1.

[0294] In certain embodiments of the carbonylation method described above, n for (1) is 0 so that the formula for (1) becomes:

##STR00323##

and the product has the formula:

##STR00324##

[0295] In certain embodiments of the carbonylation method described above, X for (3) is oxygen so that the formula for (3) becomes an epoxide:

##STR00325##

and the product has the formula:

##STR00326##

[0296] In certain embodiments, methods of the present invention comprise treating heterocycles where R.sup.a, R.sup.b, and R.sup.c are H, and R.sup.d comprises an optionally substituted C.sub.1-20 aliphatic group. In certain embodiments, methods of the present invention comprise treating heterocycles where R.sup.a, R.sup.b, R.sup.c, and R.sup.e are all H. In certain embodiments, methods of the present invention comprise treating heterocycles where R.sup.a, R.sup.b, and R.sup.c are H, and R.sup.d comprises an optionally substituted C.sub.1-6 aliphatic group. In certain embodiments, methods of the present invention comprise treating heterocycles where R.sup.a, R.sup.b, and R.sup.c are H, and R.sup.d is methyl. In certain embodiments, methods of the present invention comprise treating heterocycles where R.sup.a, R.sup.b, and R.sup.c are H, and R.sup.d is CH.sub.2Cl. In certain embodiments, methods of the present invention comprise treating heterocycles where R.sup.a, R.sup.b, and R.sup.c are H, and R.sup.d is CH.sub.2OR.sup.y, CH.sub.2OC(O)R.sup.y, where R.sup.y is as defined above. In certain embodiments, methods of the present invention comprise treating heterocycles where R.sup.a, R.sup.b, and R.sup.c are H, and R.sup.d is CH.sub.2CH(R.sup.c)OH, where R.sup.c is as defined above and in the classes and subclasses herein.

[0297] In certain embodiments, methods of the present invention comprise the step of contacting ethylene oxide with carbon monoxide in the presence of any of the catalysts defined hereinabove or described in the classes, subclasses and Tables herein. In certain embodiments, the method comprises treating the ethylene oxide with carbon monoxide in the presence of the catalyst until a substantial portion of the ethylene oxide has been converted to beta propiolactone. In certain embodiments, the method comprises treating the ethylene oxide with carbon monoxide in the presence of the catalyst until a substantial portion of the ethylene oxide has been converted to succinic anhydride.

[0298] In certain embodiments, methods of the present invention comprise the step of contacting propylene oxide with carbon monoxide in the presence of any of the catalysts defined hereinabove or described in the classes, subclasses and Tables herein. In certain embodiments, the method comprises treating the propylene oxide with carbon monoxide in the presence of the catalyst until a substantial portion of the propylene oxide has been converted to beta butyrolactone. In certain embodiments, the method comprises treating the ethylene oxide with carbon monoxide in the presence of the catalyst until a substantial portion of the propylene oxide has been converted to methyl succinic anhydride.

[0299] In another embodiment, the present invention encompasses methods of making copolymers of epoxides and CO by contacting an epoxide with CO in the presence of any of the catalysts defined hereinabove or described in the classes, subclasses and Tables herein. In certain embodiments, such processes conform to the scheme:

##STR00327##

[0300] where each of R.sup.a, R.sup.b, R.sup.c, and R.sup.d, are as defined above.

[0301] In certain embodiments, methods of the present invention comprise the step of contacting ethyle oxide with carbon monoxide in the presence of any of the catalysts defined hereinabove or described in the classes, subclasses and Tables herein to provide polypropiolactone polymer.

[0302] In certain embodiments, methods of the present invention comprise the step of contacting ethyle oxide with carbon monoxide in the presence of any of the catalysts defined hereinabove or described in the classes, subclasses and Tables herein to provide poly-3-hydroxybutyrate polymer.

[0303] In other embodiments, the present invention includes methods for carbonylation of epoxides, aziridines, thiiranes, oxetanes, lactones, lactams and analogous compounds using the above-described catalysts. Suitable methods and reaction conditions for the carbonylation of such compounds are disclosed in Yutan et al. (J. Am. Chem. Soc. 2002, 124, 1174-1175), Mahadevan et al. (Angew. Chem. Int. Ed. 2002, 41, 2781-2784), Schmidt et al. (Org. Lett. 2004, 6, 373-376 and J. Am. Chem. Soc. 2005, 127, 11426-11435), Kramer et al. (Org. Lett. 2006, 8, 3709-3712 and Tetrahedron 2008, 64, 6973-6978) and Rowley et al. (J. Am. Chem. Soc. 2007, 129, 4948-4960, in U.S. Pat. No. 6,852,865 and in U.S. patent application Ser. No. 11/705,528, all of which are hereby incorporated herein in their entirety.

EXAMPLES

Example 1

[0304] A typical route to a salen aluminum (III) catalyst is shown in Scheme E1, below:

##STR00328##

[0305] 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-benzenediamine) to afford Schiff base E1-c. This compound is then reacted with diethyl aluminum chloride and sodium cobalt tetracarbonyl to give the active Al(III)-salen 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, though in some cases routine experimentation to determine acceptable reaction conditions and functional group protection strategies may be required.

Example 2

Synthesis of [{tetrakis-(N-methyl-4-pyridinium)-porphyrin}Al(THF).SUB.2.][Co(CO).SUB.4.].SUB.5 .is shown in Scheme E2, below:

[0306] ##STR00329##

[0307] As shown in Scheme E2, pyrrole, pyridine-4-carbaldehyde and salicylic acid are refluxed in xylene to give porphyrin E2-a. E2-a is further reacted with MeCl to afford E2-b. E2-b is reacted with diethyl aluminum chloride and then with five equivalents of NaCo(CO).sub.4 in THF to afford the active Al(III)-salen catalyst E2-d. One skilled in the art of organic synthesis can adapt this chemistry as needed to provide the specific catalysts described herein, though in some cases routine experimentation to determine acceptable reaction conditions and functional group protection strategies may be required.

[0308] This application refers to various issued patents, published patent applications journal articles, and other publications all of which are incorporated herein by reference.

Other Embodiments

[0309] The foregoing has been a description of certain non-limiting embodiments of the invention. Accordingly, it is to be understood that the embodiments of the invention herein described are merely illustrative of the application of the principles of the invention. Reference herein to details of the illustrated embodiments is not intended to limit the scope of the claims, which themselves recite those features regarded as essential to the invention.