Catalysts for polycarbonate production

Abstract

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

Claims

1. A metal complex ##STR00117## wherein X is present and an anion.

2. The metal complex of claim 1, wherein X is a nucleophile capable of ring opening an epoxide.

3. The metal complex of claim 1, wherein X is selected from the group consisting of: acetate, trifluoroacetate, chloride, bromide, nitrate, carbonate, benzoate, and azide.

4. A method of catalyzing the reaction of an epoxide with carbon dioxide, comprising the step of contacting an epoxide with a metal complex of claim 1 in the presence of carbon dioxide.

Description

DETAILED DESCRIPTION OF CERTAIN EMBODIMENTS

(1) The present invention provides, among other things, a unimolecular metal complex comprising a metal atom, an optionally present anion, a ligand comprising a tethered activating moiety, and a nitrogen atom that is both: i) singly bonded to a secondary carbon which is further covalently bonded to two phenol groups ortho to their phenolic oxygens, and ii) doubly bonded to a primary carbon which is further covalently bonded to one phenol group ortho to its phenolic oxygen,
wherein all phenolic oxygens are optionally and independently substituted with either an alkyl group or a hydroxyl protecting group and where phenolic oxygens that are unsubstituted can bind the metal atom.

(2) In some embodiments, the nitrogen, the secondary carbon, and the two phenol groups to which the secondary carbon is further covalently bonded to are derived from an aminodiphenylmethane. In certain embodiments, the primary carbon and the one phenol group to which the primary carbon is further covalently bonded to are derived from a salicylaldehyde.

(3) In some embodiments, provided metal complexes have the formula I:

(4) ##STR00001##
wherein:

(5) M is a metal atom;

(6) X is optionally present and when present is an anion;

(7) ##STR00002##
comprises a ligand having the formula:

(8) ##STR00003## wherein each R.sup.d is independently selected from the group consisting of: (Z).sub.m, hydrogen, halogen, —OR, NR.sub.2, —SR, —CN, —NO.sub.2, —SO.sub.2R, —SOR, —SO.sub.2NR.sub.2, —CNO, —CO.sub.2R, —CON(R).sub.2, —OC(O)NR.sub.2, —OC(O)OR, —NRSO.sub.2R, —NCO, —N.sub.3, —SiR.sub.3, or an optionally substituted radical independently selected from the group consisting of C.sub.1-20 aliphatic, C.sub.1-20 heteroaliphatic, phenyl, a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7- to 14-membered saturated, partially unsaturated or aromatic polycyclic carbocycle, a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur, where two or more R.sup.d groups may be taken together to form one or more optionally substituted rings optionally containing one or more heteroatoms; each R is independently hydrogen or an optionally substituted radical selected the group consisting of acyl, C.sub.1-20 aliphatic, C.sub.1-20 heteroaliphatic, phenyl, a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7- to 14-membered saturated, partially unsaturated or aromatic polycyclic carbocycle, a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur, an oxygen protecting group, and a nitrogen protecting group, where two R groups on the same nitrogen atom can optionally be taken together to form an optionally substituted 3- to 7-membered ring; each n is independently an integer 1 to 4 inclusive; each R.sup.z is optionally present and when present is independently alkyl or a hydroxyl protecting group, wherein the ligand has zero or one R.sup.z groups; and (Z).sub.m represents a tethered activating moiety covalently bonded to the ligand at any suitable position, wherein each represents a linker moiety, each Z independently comprises a nitrogen or phosphorous containing functional group, and m is an integer of one or greater indicating how many such nitrogen or phosphorous containing functional groups are attached to a given linker.

Metals

(9) In some embodiments, M is a metal atom of oxidation state +3 or +4. In some embodiments, M is a metal atom of oxidation state +3. In some embodiments, M is a metal atom of oxidation state +4. In some embodiments, M is a metal atom selected from the group consisting of: Al, Co, Cr, Fe, Mn, Mo, Pt, Ti, Sn, V, and Zr. In some embodiments, M is a metal atom selected from the group consisting of: Al, Co, Cr, and Fe. In some embodiments, M is a metal atom selected from the group consisting of: Mn, Mo, Pt, Ti, Sn, V, and Zr. In some embodiments, M is Al. In some embodiments, M is Co. In some embodiments, M is Cr. In some embodiments, M is Fe.

Anions

(10) In some embodiments, X is absent. In some embodiments, X is present and is an anion. In some embodiments, X is a nucleophile capable of ring opening an epoxide. In some embodiments, X is selected from the group consisting of halide, a complex inorganic ion (e.g., perchlorate), borates, sulfonates, sulfates, phosphates, phenolates, carbonates, and carboxylates. In some embodiments, X is selected from the group consisting of halide, hydroxide, carboxylate, sulfate, phosphate, —OR.sup.x, —O(C═O)R.sup.x, —NC, —CN, —NO.sub.3, —N.sub.3, —O(SO.sub.2)R.sup.x and —OP(R.sup.x).sub.3, wherein each R.sup.x is, independently, selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl and optionally substituted heteroaryl. In some embodiments, X is selected from the group consisting of: acetate, trifluoroacetate, chloride, bromide, nitrate, carbonate, benzoate, and azide.

Chelation and Phenolic Oxygen Substitution (R.SUP.z.)

(11) In some embodiments, the ligand has zero R.sup.z groups. In some embodiments, the ligand has one R.sup.z group. In some embodiments, R.sup.z is alkyl. In some embodiments, R.sup.z is methyl. In some embodiments, R.sup.z is a hydroxyl protecting group.

(12) In some embodiments of provided metal complexes, a

(13) ##STR00004##
moiety has a formula selected from Formulae Ia, Ib, Ic, or Id:

(14) ##STR00005##
wherein each of M, X, R.sup.d, n, and R.sup.z are as defined above and described in classes and subclasses herein, both singly and in combination.

Tether Position (R.SUP.d.)

(15) In some embodiments of the above formulae, n is 0 for one, two, or three instances of (R.sup.d).sub.n. In some embodiments of the above formulae, n is 1 for one, two, or three instances of (R.sup.d).sub.n. In some embodiments of the above formulae, n is 2 for one, two, or three instances of (R.sup.d).sub.n. In some embodiments of the above formulae, n is 3 for one, two, or three instances of (R.sup.d).sub.n. In some embodiments of the above formulae, n is 4 for one, two, or three instances of (R.sup.d).sub.n. In some embodiments of the above formulae, n is 2 for one instances of (R.sup.d).sub.n, and n is 0 for the other instances of (R.sup.d).sub.n

(16) In some embodiments of the above formulae, each phenolic ring portion of a metal complex independently comprises a substructure:

(17) ##STR00006##
wherein: each R.sup.4a, R.sup.5a, R.sup.6a, and R.sup.7a is independently selected from the group consisting of: (Z).sub.m, hydrogen, halogen, —OR, NR.sub.2, —SR, —CN, —NO.sub.2, —SO.sub.2R, —SOR, —SO.sub.2NR.sub.2, —CNO, —CO.sub.2R, —CON(R).sub.2, —OC(O)NR.sub.2, —OC(O)OR, —NRSO.sub.2R, —NCO, —N.sub.3, or an optionally substituted radical selected from the group consisting of C.sub.1-20 aliphatic, C.sub.1-20 heteroaliphatic, phenyl, a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7- to 14-membered saturated, partially unsaturated or aromatic polycyclic carbocycle, a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur, wherein any two adjacent R.sup.4a, R.sup.5a, R.sup.6a, and R.sup.7a groups may be taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more heteroatoms; and wherein (Z).sub.m and R are as defined above and described in classes and subclasses herein, both singly and in combination.

(18) In some embodiments, R.sup.4a, R.sup.5a, R.sup.6a, and R.sup.7a are each hydrogen. In some embodiments, R.sup.4a, R.sup.6a, and R.sup.7a are each hydrogen. In some embodiments, R.sup.4a and R.sup.6a are each hydrogen. In some embodiments, R.sup.5a and R.sup.7a are independently selected from the group consisting of (Z).sub.m, hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, t-butyl, isoamyl, t-amyl, thexyl, and trityl. In some embodiments, one or both of R.sup.5a and R.sup.7a is a (Z).sub.m group. In some embodiments, R.sup.7a is selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, t-butyl, isoamyl, t-amyl, thexyl, and trityl. In some embodiments, R.sup.5a is a (Z).sub.m group.

(19) In some embodiments, a phenolic ring portion of a metal complex comprises a substructure selected from the group consisting of:

(20) ##STR00007## ##STR00008##
wherein (Z).sub.m is as defined above and described in classes and subclasses herein, both singly and in combination.

(21) In some embodiments, R.sup.5a is selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, t-butyl, isoamyl, t-amyl, thexyl, and trityl. In some embodiments, R.sup.7a is a (Z).sub.m group. In some embodiments, a phenolic ring portion of a metal complex comprises a substructure selected from the group consisting of:

(22) ##STR00009## ##STR00010##
wherein (Z).sub.m is as defined above and described in classes and subclasses herein, both singly and in combination.

(23) In some embodiments, R.sup.4a, R.sup.5a, and R.sup.7a are each hydrogen. In some embodiments, R.sup.4a and R.sup.5a are each hydrogen. In some embodiments, R.sup.4a and R.sup.7a are each hydrogen. In some embodiments, R.sup.4a is hydrogen. In some embodiments, R.sup.4a and R.sup.6a are independently selected from the group consisting of (Z).sub.m, hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, t-butyl, isoamyl, t-amyl, thexyl, and trityl. In some embodiments, one or both of R.sup.4a and R.sup.6a is a (Z).sub.m group. In some embodiments, R.sup.5a and R.sup.7a are each independently selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, t-butyl, isoamyl, t-amyl, thexyl, and trityl. In some embodiments, R.sup.5a is selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, t-butyl, isoamyl, t-amyl, thexyl, and trityl. In some embodiments, R.sup.7a is selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, t-butyl, isoamyl, t-amyl, thexyl, and trityl. In some embodiments, R.sup.6a is a (Z).sub.m group. In some embodiments, a phenolic ring portion of a metal complex comprises a substructure selected from the group consisting of:

(24) ##STR00011## ##STR00012## ##STR00013## ##STR00014##
wherein (Z).sub.m is as defined above and described in classes and subclasses herein, both singly and in combination.

(25) In some embodiments, R.sup.5a, R.sup.6a, and R.sup.7a are each hydrogen. In some embodiments, R.sup.5a and R.sup.6a are each hydrogen. In some embodiments, R.sup.6a and R.sup.7a are each hydrogen. In some embodiments, R.sup.6a is hydrogen. In some embodiments, R.sup.4a is a (Z).sub.m group. In some embodiments, a phenolic ring portion of a metal complex comprises a substructure selected from the group consisting of:

(26) ##STR00015## ##STR00016## ##STR00017## ##STR00018##
wherein (Z).sub.m is as defined above and described in classes and subclasses herein, both singly and in combination.

(27) In some embodiments of the above formulae under this heading “Tethering Position (R.sup.d)” at least one of the phenyl rings is derived from a salicylaldehyde. In some embodiments, at least one activating moiety is tethered to a carbon atom of a phenyl ring of the salicylaldehyde-derived portion of a ligand. In some embodiments, two of the phenyl rings are derived from an aminodiphenylmethane.

Linker

(28) In certain embodiments, each linker moiety comprises 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.

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

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

(31) In certain embodiments, 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, 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.

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

(33) In certain embodiments, is selected from the group consisting of:

(34) ##STR00019## ##STR00020## ##STR00021##
* represents the site of attachment to a ligand, and each # represents a site of attachment of an activating functional group.

(35) 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.

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

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

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

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

(40) ##STR00022##
where R.sup.1, *, s, and Z are as defined above. In certain embodiments, an activating moiety

(41) (Z).sub.m has a formula

(42) ##STR00023##
where *, s, and Z are as defined above. In certain embodiments, an activating moiety (Z).sub.m has a formula

(43) ##STR00024##
where *, s, and Z are as defined above and described in classes and subclasses herein. In certain embodiments, an activating moiety (Z).sub.m has a formula selected from the group consisting of:

(44) ##STR00025##
where Z and * are as defined above and described in classes and subclasses herein.

(45) In certain embodiments, an activating moiety (Z).sub.m has a formula selected from the group consisting of:

(46) ##STR00026##
where Z, and * are as defined above and described in classes and subclasses herein.

(47) In certain embodiments, an activating moiety (Z).sub.m has a formula selected from the group consisting of:

(48) ##STR00027##
where *, #, and s are as defined above and described in classes and subclasses herein. In certain embodiments, an activating moiety (Z).sub.m has a formula selected from the group consisting of:

(49) ##STR00028## ##STR00029##
where Z, and * are as defined above and described in classes and subclasses herein.

(50) In certain embodiments, an activating moiety (Z).sub.m has a formula selected from the group consisting of:

(51) ##STR00030##
where Z and * are as defined above and described in classes and subclasses herein.

Activating Groups ((Z).SUB.m.)

(52) In some embodiments, each activating functional group is independently selected from the group consisting of neutral nitrogen-containing moieties, cationic moieties, phosphorous-containing moieties, and combinations of two or more of these. In some embodiments, an activating group has no free amines. The term “no free amines”, as used herein, refers to a nitrogen-containing group having no nitrogen atoms bearing a hydrogen in any tautomeric or resonance form.

(53) In some embodiments of (Z).sub.m, m is 1. In some embodiments m is 2.

Neutral Nitrogen-Containing Activating Groups

(54) In some embodiments, one or more Z groups on provided metal complexes are neutral nitrogen-containing moieties. In some embodiments, such neutral nitrogen-containing moieties include one or more of the structures in Table Z-1:

(55) TABLE-US-00001 TABLE Z-1
wherein: each R.sup.1, R.sup.2, and R.sup.3 is independently hydrogen or an optionally substituted radical selected from the group consisting of C.sub.1-20 aliphatic, C.sub.1-20 heteroaliphatic, 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 two or more R.sup.1 and R.sup.2 groups can be taken together to form one or more optionally substituted rings optionally containing one or more additional heteroatoms, and 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 each R.sup.4 is independently hydrogen, a hydroxyl protecting group, or an optionally substituted radical selected from the group consisting of C.sub.1-20 acyl, C.sub.1-20 aliphatic, C.sub.1-20 heteroaliphatic, 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.4 can be taken together to form one or more optionally substituted heterocyclic or heteroaryl rings optionally containing one or more additional heteroatoms.

(56) 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, 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, phenyl, 8- to 10-membered aryl, and 3- to 7-membered heterocyclic having 1-2 heteroatoms independently selected from nitrogen, oxygen, or sulfur. 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.

(57) 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.

(58) 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.

(59) 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.1-20 heteroaliphatic, 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, 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.

(60) 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.

(61) 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.

(62) In certain embodiments, each R.sup.1 and R.sup.2 are hydrogen. In some embodiments, each R.sup.1 is hydrogen 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.

(63) 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.

(64) In some embodiments, two or more R.sup.1 and R.sup.2 are taken together 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 ring fragment 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.

(65) In certain embodiments, R.sup.3 is hydrogen. 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.

(66) 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.

(67) In some embodiments, two or more R.sup.1 or R.sup.2 groups are taken together with R.sup.3 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.

(68) In certain embodiments, R.sup.4 is hydrogen. In some embodiments, R.sup.4 is an optionally substituted radical selected from the group consisting of C.sub.1-12 aliphatic, phenyl, 8- to 10-membered aryl, and 3- to 8-membered heterocyclic. In certain embodiments, R.sup.4 is C.sub.1-12 aliphatic. In certain embodiments, R.sup.4 is C.sub.1-6 aliphatic. In some embodiments, R.sup.4 is an optionally substituted 8- to 10-membered aryl group. In certain embodiments, R.sup.4 is optionally substituted C.sub.1-12 acyl or optionally substituted C.sub.1-6 acyl. In certain embodiments, R.sup.4 is optionally substituted phenyl. In some embodiments, R.sup.4 is a hydroxyl protecting group. In some embodiments, R.sup.4 is a hydroxyl protecting group containing a silyl group. In some embodiments, R.sup.4 is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, allyl, phenyl, or benzyl.

(69) In certain embodiments, R.sup.1 and R.sup.4 are taken together with intervening atoms to form one or more optionally substituted heterocyclic or heteroaryl rings optionally containing one or more additional heteroatoms.

(70) In some embodiments, an activating functional group is an N-linked amino group. In some embodiments, an activating functional group is an N-linked amino group of the formula:

(71) ##STR00037##
wherein R.sup.1 and R.sup.2 are as defined above and described in classes and subclasses herein, both singly and in combination.

(72) In some embodiments, an N-linked amino activating functional group is selected from the group consisting of:

(73) ##STR00038## ##STR00039## ##STR00040##

(74) In some embodiments, an activating functional group is an N-linked hydroxyl amine. In some embodiments, an activating functional group is an N-linked hydroxyl amine of the formula:

(75) ##STR00041##
wherein R.sup.1 and R.sup.4 are as defined above and described in classes and subclasses herein, both singly and in combination. In certain embodiments, one or more N-linked hydroxyl amine activating functional groups are selected from the group consisting of:

(76) ##STR00042##

(77) In some embodiments, an activating functional group is an amidine. In some embodiments, an activating functional group is an amidine is selected from the group consisting of:

(78) ##STR00043##
wherein each of R.sup.1, R.sup.2, and R.sup.3 is as defined above and described in classes and subclasses herein, both singly and in combination. In some embodiments, an activating functional group is an N-linked amidine. In some embodiments, an activating functional group is an N-linked amidine of the formula:

(79) ##STR00044##
wherein each of R.sup.1, R.sup.2, and R.sup.3 is as defined above and described in classes and subclasses herein, both singly and in combination. In certain embodiments, such N-linked amidine groups are selected from the group consisting of:

(80) ##STR00045##

(81) In some embodiments, an activating functional group is an amidine moiety linked through the imine nitrogen. In some embodiments, an activating functional group is an amidine moiety linked through the imine nitrogen and of the formula:

(82) ##STR00046##
wherein 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, such imine-linked amidine activating functional groups are selected from the group consisting of:

(83) ##STR00047## ##STR00048##

(84) In some embodiments, an activating functional group is an amidine moiety linked through a carbon atom. In some embodiments, an activating functional group is an amidine moiety linked through a carbon atom and of the formula:

(85) ##STR00049##
wherein each of R.sup.1, R.sup.2, and R.sup.3 is as defined above and described in classes and subclasses herein, both singly and in combination. In certain embodiments, such carbon-linked amidine activating groups are selected from the group consisting of:

(86) ##STR00050## ##STR00051##

(87) In some embodiments, an activating functional group is a carbamate. In some embodiments, an activating functional group is a N-linked carbamate. In some embodiments, an activating functional group is a N-linked carbamate of the formula:

(88) ##STR00052##

(89) wherein each of R.sup.1 and R.sup.2 is as defined above and described in classes and subclasses herein, both singly and in combination.

(90) In some embodiments, an activating functional group is a O-linked carbamate In some embodiments, an activating functional group is a O-linked carbamate of the formula:

(91) ##STR00053##
wherein each of R.sup.1 and R.sup.2 is as defined above and described in classes and subclasses herein, both singly and in combination.

(92) In some embodiments of such carbamates, R.sup.2 is selected from the group consisting of: methyl, t-butyl, t-amyl, benzyl, adamantyl, allyl, 4-methoxycarbonylphenyl, 2-(methyl sulfonyl)ethyl, 2-(4-biphenylyl)-prop-2-yl, 2-(trimethylsilyl)ethyl, 2-bromoethyl, and 9-fluorenylmethyl.

(93) In some embodiments, an activating functional group is a guanidine or bis-guanidine group. In some embodiments, an activating functional group is a guanidine or bis-guanidine selected from the group consisting of:

(94) ##STR00054##
wherein each R.sup.1 and R.sup.2 is as defined above and described in classes and subclasses herein, both singly and in combination. In some embodiments of such guanidines or bis-guanidines, 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 polycyclic heterocycle ring system. In certain embodiments, where an activating functional group is a guanidine or bis guanidine moiety, it is selected from the group consisting of:

(95) ##STR00055## ##STR00056##

(96) In some embodiments, an activating functional group is a urea. In some embodiments, an activating functional group is a urea of the formula:

(97) ##STR00057##
wherein each R.sup.1 and R.sup.2 is independently as defined above and described in classes and subclasses herein, both singly and in combination.

(98) In some embodiments, an activating functional group is an oxime or hydrazone group. In some embodiments, an activating functional group an oxime or hydrazone group of the formula:

(99) ##STR00058##
wherein each of R.sup.1, R.sup.2, R.sup.3, and R.sup.4 is as defined above and described in classes and subclasses herein, both singly and in combination.

(100) In some embodiments, an activating functional group is a N-oxide derivative. In some embodiments, an activating functional group is a N-oxide derivative is of the formula:

(101) ##STR00059##
wherein each of R.sup.1 and R.sup.2 is as defined above and described in classes and subclasses herein, both singly and in combination. In certain embodiments, an N-oxide activating functional group is selected from the group consisting of:

(102) ##STR00060## ##STR00061##

Cationic Activating Groups

(103) In some embodiments, one or more tethered activating functional groups on provided metal complexes comprise a cationic moiety. In some embodiments, a cationic moiety is selected from a structure in Table Z-2:

(104) TABLE-US-00002 TABLE Z-2 0
wherein: each of R.sup.1, R.sup.2, and R.sup.3 is independently as defined above and described in classes and subclasses herein, both singly and in combination; R.sup.5 is R.sup.2 or hydroxyl; wherein R.sup.1 and R.sup.5 can be taken together 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 to form one or more optionally substituted rings optionally containing one or more heteroatoms, and an R.sup.6 and R.sup.7 group can be taken with an R.sup.1 or R.sup.2 group to form one or more optionally substituted rings; each occurrence of R.sup.8 is independently selected from the group consisting of: halogen, —NO.sub.2, —CN, —SR.sup.y, —S(O)R.sup.y, —S(O).sub.2R.sup.y, —NR.sup.yC(O)R.sup.y, —OC(O)R.sup.y, —CO.sub.2R.sup.y, —NCO, —N.sub.3, —OR.sup.7, —OC(O)N(R.sup.y).sub.2, —N(R.sup.3).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, both singly and in combination, and where two or more adjacent R.sup.8 groups can be taken together to form an optionally substituted saturated, partially unsaturated, or aromatic 5- to 12-membered ring containing 0 to 4 heteroatoms; X.sup.− is any anion; Ring A is an optionally substituted, 5- to 10-membered heteroaryl group; and Ring B is an optionally substituted, 3- to 8-membered saturated or partially unsaturated monocyclic heterocyclic ring having 0-2 heteroatoms in addition to the depicted ring nitrogen atom independently selected from nitrogen, oxygen, or sulfur.

(105) It will be appreciated that when X.sup.− is present as a counterion to a cationic activating group, such X may be the same or different as an X bonded to the metal atom of the metal complex.

(106) In some embodiments, an activating functional group is a protonated amine. In some embodiments, an activating functional group is a protonated amine of the formula:

(107) ##STR00077##
wherein each of R.sup.1 and R.sup.2 is as defined above and described in classes and subclasses herein, both singly and in combination. In some embodiments, a protonated amine activating functional group is selected from the group consisting of:

(108) ##STR00078## ##STR00079##

(109) In some embodiments, an activating functional group is a quaternary amine. In some embodiments, an activating functional group is a quaternary amine of the formula:

(110) ##STR00080##
wherein each of R.sup.1, R.sup.2, and R.sup.3 is as defined above and described in classes and subclasses herein, both singly and in combination. In some embodiments of such quaternary amines, R.sup.1, R.sup.2, and R.sup.3 are C.sub.1-C.sub.6 alkyl. In some embodiments, R.sup.1, R.sup.2, and R.sup.3 are t-butyl. In some embodiments, R.sup.1, R.sup.2, and R.sup.3 are sec-butyl. In some embodiments, R.sup.1, R.sup.2, and R.sup.3 are n-butyl. In some embodiments, R.sup.1, R.sup.2, and R.sup.3 are i-propyl. In some embodiments, R.sup.1, R.sup.2, and R.sup.3 are n-propyl. In some embodiments, R.sup.1, R.sup.2, and R.sup.3 are ethyl. In some embodiments, R.sup.1, R.sup.2, and R.sup.3 are methyl.

(111) In some embodiments, an activating functional group is a guanidinium group. In some embodiments, an activating group is a guanidinium group of the formula:

(112) ##STR00081##
wherein each R.sup.1 and R.sup.2 is independently as defined above and described in classes and subclasses herein, both singly and in combination. In some embodiments of such guanidiniums, 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. In some embodiments, any two or more R.sup.1 or R.sup.2 groups are taken together 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 polycyclic heterocyclic ring system. In certain embodiments, a R.sup.1 and R.sup.2 group are taken together with intervening atoms to form a group selected from:

(113) ##STR00082##
wherein each R.sup.1 and R.sup.2 is independently as defined above and described in classes and subclasses herein, both singly and in combination, and Ring G is an optionally substituted 5- to 7-membered saturated or partially unsaturated heterocyclic ring.

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

(115) ##STR00083##

(116) In some embodiments, an activating functional group is a cationic bicyclic guanidinium group, wherein the cationic bicyclic guanidinium group has no free amines. In some embodiments, a guanidinium group having no free amines has two nitrogen atoms each bearing three nonhydrogen substituents and a third nitrogen atom with bonds to four nonhydrogen substituents. In some embodiments, such nonhydrogen substituents are aliphatic substituents. In some embodiments, a guanidinium group having no free amines is cationic, as compared to a neutral guanidinium group having a free amine.

(117) It will be appreciated that when a guanidinium cation is drawn in a particular fashion herein, all resonance or tautomeric forms are contemplated and encompassed by the present disclosure. For example, the group:

(118) ##STR00084##
may also be depicted as

(119) ##STR00085##

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

(121) ##STR00086##
wherein R.sup.1 is as defined above and described in classes and subclasses herein, both singly and in combination. In some embodiments, R.sup.1 is methyl and the activating functional group is selected from the group consisting of:

(122) ##STR00087##

(123) In some embodiments, an activating function group is an amidinium group. In some embodiments, an activating functional group is an amidinium group of the formula:

(124) ##STR00088##
wherein each R.sup.1, R.sup.2, and R.sup.3 is independently as defined above and described in classes and subclasses herein, both singly and in combination. In some embodiments, an activating functional group an amidinium group of the formula:

(125) ##STR00089##
wherein each R.sup.1 and R.sup.2 is independently as defined above and described in classes and subclasses herein, both singly and in combination.

(126) In some embodiments, an activating functional group is a cationic bicyclic amidinium group, wherein the cationic bicyclic amidinium group has no free amines. In some embodiments, an amidinium group having no free amines has one nitrogen atom bearing three nonhydrogen substituents and a second nitrogen atom with bonds to four nonhydrogen substituents. In some embodiments, such nonhydrogen substituents are aliphatic substituents. In some embodiments, such nonhydrogen substituents comprise the rings of the bicyclic amidinium group. In some embodiments, an amidinium group having no free amines is cationic, as compared to a neutral amidinium group having a free amine.

(127) It will be appreciated that when an amidinium cation is drawn in a particular fashion herein, all resonance forms are contemplated and encompassed by the present disclosure. For example, the group:

(128) ##STR00090##
may also be depicted as

(129) ##STR00091##

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

(131) ##STR00092##

(132) In some embodiments, an activating functional group is or comprises an optionally substituted nitrogen-containing heterocycle or heteroaryl. In certain embodiments, the nitrogen-containing heterocycle is heteroaryl. In certain embodiments, an 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.

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

(134) In certain embodiments, a nitrogen-containing heterocycle or heteroaryl 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 N—H bond and the nitrogen atom thereby remains neutral. In certain embodiments, an optionally substituted N-linked nitrogen-containing heteroaryl is a pyridinium derivative. In certain embodiments, an optionally substituted N-linked nitrogen-containing heteroaryl is an imidazolium derivative. In certain embodiments, an optionally substituted N-linked nitrogen-containing heteroaryl is a thiazolium derivative. In certain embodiments, an optionally substituted N-linked nitrogen-containing heteroaryl is a oxazolium derivative.

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

(136) ##STR00093##

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

(138) ##STR00094##

(139) 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.

(140) In some embodiments, a nitrogen-containing heterocycle or heteroaryl activating functional group is selected from the group consisting of:

(141) ##STR00095## ##STR00096##

(142) 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.

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

(144) ##STR00097##
wherein each R.sup.1, R.sup.2, and R.sup.3 is independently as defined above and described in classes and subclasses herein, both singly and in combination.

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

(146) ##STR00098##
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, both singly and in combination.

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

(148) ##STR00099##
wherein each R.sup.1 and R.sup.2 is independently as defined above and described in classes and subclasses herein, both singly and in combination.

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

(150) ##STR00100##
wherein each R.sup.1, R.sup.2, and R.sup.3 is independently as defined above and described in classes and subclasses herein, both singly and in combination.

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

(152) ##STR00101##
wherein each R.sup.1 and R.sup.2 is independently as defined above and described in classes and subclasses herein, both singly and in combination.

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

(154) ##STR00102##
wherein each R.sup.1 and R.sup.2 is independently as defined above and described in classes and subclasses herein, both singly and in combination.

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

(156) ##STR00103##
wherein each R.sup.1, R.sup.2, and R.sup.3 is independently as defined above and described in classes and subclasses herein, both singly and in combination.

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

(158) ##STR00104##
wherein each R.sup.1 and R.sup.2 is independently as defined above and described in classes and subclasses herein, both singly and in combination.

(159) In some embodiments, an activating functional group is a sulfonium group or an arsonium group. In some embodiments, an activating functional group is a sulfonium group or an arsonium group of the formula:

(160) ##STR00105##
wherein each of R.sup.1, R.sup.2, and R.sup.3 are as defined above and described in classes and subclasses herein, both singly and in combination. In some embodiments, an arsonium activating functional group is selected from the group consisting of:

(161) ##STR00106##

Phosphorous-Containing Activating Groups

(162) In some embodiments, activating functional groups Z are phosphorous containing groups. In certain embodiments, a phosphorous-containing functional group is chosen from the group consisting of: phosphines (—PR.sup.y.sub.2); Phosphine oxides (—P(O)R.sup.y.sub.2); phosphinites (—P(OR.sup.4)R.sup.y.sub.2); phosphonites (—P(OR.sup.4).sub.2R.sup.y); phosphites (—P(OR.sup.4).sub.3); phosphinates (—OP(OR.sup.4)R.sup.y.sub.2); phosphonates; (—OP(OR.sup.4).sub.2R.sup.y); phosphates (—OP(OR.sup.4).sub.3); and phosphonium salts ([—PR.sup.y.sub.3].sup.+) where a phosphorous-containing functional group may be linked to a metal complex through any available position (e.g. direct linkage via the phosphorous atom, or in some cases via an oxygen atom).

(163) In certain embodiments, a phosphorous-containing functional group is chosen from the group consisting of:

(164) ##STR00107##
wherein each R.sup.1, R.sup.2, and R.sup.4 is as defined above and described in classes and subclasses herein, both singly and in combination; and where two R.sup.4 groups can be taken together with intervening atoms to form an optionally substituted ring optionally containing one or more heteroatoms, or an R.sup.4 group can be taken with an R.sup.1 or R.sup.2 group to an optionally substituted carbocyclic, heterocyclic, heteroaryl, or aryl ring.

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

(166) In certain embodiments, phosphorous-containing functional groups have the formula:
—(V).sub.b—[(R.sup.9R.sup.10R.sup.11P).sup.+].sub.nW.sup.n−,
wherein: V is —O—, —N═, or —NR.sup.z—; b is 1 or 0; each of R.sup.9, R.sup.10 and R.sup.11 are independently present or absent and, if present, are independently selected from the group consisting of optionally substituted C.sub.1-C.sub.20 aliphatic, optionally substituted phenyl, optionally substituted C.sub.8-C.sub.14 aryl, optionally substituted 3- to 14-membered heterocyclic, optionally substituted 5- to 14-membered heteroaryl, halogen, ═O, —OR.sup.z, ═NR.sup.z and N(R.sup.z).sub.2 where R.sup.z is hydrogen, or an optionally substituted C.sub.1-C.sub.20 aliphatic, optionally substituted phenyl, optionally substituted 8- to 14-membered aryl, optionally substituted 3- to 14-membered heterocyclic, or optionally substituted 5- to 14-membered heteroaryl; W is any anion; and n is an integer between 1 and 4.

(167) In certain embodiments, an activating functional group is a phosphonate group. In some embodiments, an activating functional group is a phosphonate group selected from the group consisting of:

(168) ##STR00108##
wherein each R.sup.1, R.sup.2, and R.sup.4 is independently as defined above and described in classes and subclasses herein, both singly and in combination. In specific embodiments, a phosphonate activating functional group is selected from the group consisting of:

(169) ##STR00109##

(170) In some embodiments, an activating functional group is a phosphonic diamide group. In some embodiments, an activating functional group is a phosphonic diamide group selected from the group consisting of:

(171) ##STR00110##
wherein each R.sup.1, R.sup.2, and R.sup.4 is independently as defined above and described in classes and subclasses herein, both singly and in combination. In certain embodiments, each R.sup.1 and R.sup.2 group in a phosphonic diamide is methyl.

(172) In some embodiments, an activating functional group is a phosphine group. In some embodiments, an activating functional group is a phosphine group of the formula:

(173) ##STR00111##
wherein R.sup.1 and R.sup.2 are as defined above and described in classes and subclasses herein, both singly and in combination. In some embodiments, a phosphine activating functional group is selected from the group consisting of:

(174) ##STR00112##

Methods of Use

(175) In some embodiments, provided metal complexes are useful for the polymerization of epoxides and carbon dioxide. In some embodiments, the present invention provides a method comprising the step of contacting an epoxide or mixture of epoxides and carbon dioxide with a provided metal complex to form a polycarbonate polymer composition.

(176) In certain embodiments, the present invention provides a method comprising the steps of:

(177) i. contacting an epoxide and carbon dioxide with a metal complex to form a polycarbonate polymer composition; and

(178) ii. performing chromatography, filtration, or precipitation to obtain isolated polycarbonate polymer composition.

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

EXAMPLES

Example 1

(180) This example describes the synthesis of an aminodiphenylmethane used in the synthesis of a ligand for a metal complex.

(181) ##STR00113##

Example 2

(182) This example describes the synthesis of a salicylaldehyde used in the synthesis of a ligand for a metal complex. Suitable methods of performing this reaction are also disclosed in U.S. Pat. No. 6,870,004 which is incorporated herein by reference.

(183) ##STR00114##

Example 3

(184) This example describes the synthesis of metal complex A. A salicylaldehyde and an aminodiphenylmethane are reacted to yield ligand A-1. This ligand is reacted further with tin(IV) chloride to yield the metal complex.

(185) ##STR00115##

Example 4

(186) This example describes the synthesis of metal complex B. An alkylated salicylaldehyde and an aminodiphenylmethane are reacted to yield ligand B-1. This ligand is reacted further with cobalt to yield the metal complex.

(187) ##STR00116##