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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

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.

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1. A catalyst comprising: i) a metal complex of formula:  wherein: M is a metal atom;a is an integer from 1 to 4 inclusive;at least on of R1a, R1a′, R2a, R2a′, R3a, R3a′, Rc, and Rd is independently (Z+)b, wherein: is a bond or a linker;Z+comprises an atom selected from the group consisting of nitr

1. A catalyst comprising: i) a metal complex of formula:  wherein: M is a metal atom;a is an integer from 1 to 4 inclusive;at least on of R1a, R1a′, R2a, R2a′, R3a, R3a′, Rc, and Rd is independently (Z+)b, wherein: is a bond or a linker;Z+comprises an atom selected from the group consisting of nitrogen, phosphorous, arsenic, and sulfur; andb is an integer from 1 to 4 inclusive;the remaining R1a, R1a′, R2a, R2a′, R3a′ at each occurrence are independently hydrogen, halogen, —OR4, —NRy2, —CN, —NO2, —SO2Ry, —SO2NRy2, —CNO, —NCO, or —N3; or an optionally substituted group selected from the group consisting of: C1-20 aliphatic;C1-20 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; and4- to 7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;wherein:R4 at each occurrence is a hydroxyl protecting group or Ry;Ry at each occurrence is independently hydrogen, or an optionally substituted group selected from the group consisting of: acyl;carbamoyl;arylalkyl;6- to 10-membered aryl;C1-12 aliphatic;C1-12 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; anda nitrogen protecting group; orwherein two Ryon 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;wherein any of (R2a′ and R3a′), (R2a and R3a), (R1a and R2a), and (R1a′ and R2a′) may optionally be taken together with the carbon atoms to; which they are attached to form one or more rings:R4a is selected from the group consisting of  wherein: Rd at each occurrence is independently (Z+)b, hydrogen, halogen, —OR4, —NRy2, —CN, —NO2, —SO2Ry, —SORy, —SO2NRy2, —CNO, —NCO, or —N3; or an optionally substituted group selected from the group consisting of: C1-20 aliphatic;C1-20 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 the group consisting of nitrogen, oxygen, and sulfur; and4- to 7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur, orwherein two or more Rd groups are taken together to form one or more optionally substituted rings;Rc at each occurrence is independently (Z+)b, hydrogen, halogen, —NRy2, —SRy, —CN, —NO2,—SO2Ry, —SORy, —SO2NRy2, —CNO, —NCO, or —N3; or an optionally substituted group selected from the group consisting of: C1-20 aliphatic;C1-20 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; and4- to 7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; orwherein two or more Rc groups are taken together with the carbon atoms to which they are attached and any intervening atoms to form one or more rings; orwherein two Rc groups are attached to the same carbon atom, and are 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 hydrazine; andan imine:m′ is 0 or an integer from 1 to 4, inclusive; andq is 0 or an integer from 1 to 4, inclusive; andii) at least one anionic metal carbonyl species associated with at least one of Z+. 2. The catalyst of claim 1, wherein M is 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), and Mn(III). 3. The catalyst of claim 1, wherein M is aluminum. 4. The catalyst of claim 1, wherein M is chromium. 5. The catalyst of claim 1, wherein at least one anionic metal carbonyl species is X−, and X− is associated with at least on Z+, wherein Z+X− is selected from the group consisting of: or a combination of two or more of these, wherein: each R1 and R2 is independently hydrogen or an optionally substituted group selected from the group consisting of: C1-20 aliphatic;C1-20 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 the group consisting of nitrogen, oxygen, and sulfur;an 8- to 14-membered polycyclic heteroaryl ring having 1-5 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;a 3- to 8-membered saturated or partially unsaturated monocyclic heterocyclic ring having 1-3 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;a 6- to 14-membered saturated or partially unsaturated polycyclic heterocycle having 1-5 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; phenyl; andan 8- to 14-membered polycyclic aryl ring; orwherein R1 and R2 are taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more additional heteroatoms;each R3 is independently hydrogen or an optionally substituted group selected from the group consisting of: C1-20 aliphatic;C1-20 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 the group consisting of nitrogen, oxygen, and sulfur;an 8- to 14-membered polycyclic heteroaryl ring having 1-5 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;a 3- to 8-membered saturated or partially unsaturated monocyclic heterocyclic ring having 1-3 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;a 6- to 14-membered saturated or partially unsaturated polycyclic heterocycle having 1-5 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; phenyl; andan 8- to 14-membered polycyclic aryl ring; orwherein an R3 group are taken with an R1 or R2 group to form one or more optionally substituted rings; andR5 is R2 or hydroxyl; or wherein R1 and R5 are taken together with intervening atoms to form one or more optionally substituted carbocyclic, heterocyclic, aryl, or heteroaryl rings;each R6 and R7 is independently hydrogen or an optionally substituted group selected from the group consisting of: C1-20 aliphatic;C1-20 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 the group consisting of nitrogen, oxygen, and sulfur;an 8- to 14-membered polycyclic heteroaryl ring having 1-5 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;a 3- to 8-membered saturated or partially unsaturated monocyclic heterocyclic ring having 1-3 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;a 6- to 14-membered saturated or partially unsaturated polycyclic heterocycle having 1-5 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; phenyl; andan 8- to 14-membered polycyclic aryl ring; orwherein R6 and R7 are taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more heteroatoms, or an R6 and R7 group are taken with an R1 or R2 group to form one or more optionally substituted rings;each occurrence of R8 is independently: halogen, —NO2, —CN, —SRy, —S(O)Ry, —S(O)2Ry, —NRyC(O)Ry, —OC(O)Ry, —CO2Ry, —NCO, —N3, —OR7, —OC(O)N(Ry)2, —N(Ry)2, —NRyC(O)Ry, or —NRyC(O)ORy; or an optionally substituted group selected from the group consisting of: C1-20 aliphatic;C1-20 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 the group consisting of nitrogen, oxygen, and sulfur;an 8- to 14-membered polycyclic heteroaryl ring having 1-5 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;a 3- to 8-membered saturated or partially unsaturated monocyclic heterocyclic ring having 1-3 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;a 6- to 14-membered saturated or partially unsaturated polycyclic heterocycle having 1-5 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; phenyl; andan 8- to 14-membered polycyclic aryl ring; wherein each Ry is independently —H, or an optionally substituted group selected from the group consisting of C1-6 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 the group consisting of nitrogen, oxygen, and sulfur, a 5-6 membered heteroaryl ring having 1-3 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur, and an 8- to 10- membered aryl; orwherein two or more adjacent R8 groups are taken together to form an optionally substituted saturated, partially unsaturated, or aromatic 5- to 12-membered ring containing 0 to 4 heteroatoms;Ring A is an optionally substituted, 5- to 10-membered heteroaryl group; andRing 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 the group consisting of nitrogen, oxygen, and sulfur;wherein: when is a bond,  is the site of attachment of Z+ to the metal complex;when is a linker,  is the site of attachment of Z+ to the linker. 6. The catalyst of claim 5, wherein Z+X− is selected from the group consisting of: 7. The catalyst of claim 6, wherein Z+X− is selected from the group consisting of: 8. The catalyst of claim 6, wherein Z+X− is selected from the group consisting of: 9. The catalyst of claim 6, wherein Z+X− is selected from the group consisting of: 10. The catalyst of claim 1, wherein the linker 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. 11. The catalyst of claim 10, wherein the linker is an optionally substituted C2-30 aliphatic group wherein one or more methylene units are optionally and independently replaced by: —Cy-, —NRy—, —N(Ry)C(O)—, —C(O)N(Ry)—, —O—, —C(O)—, —OC(O)—, —C(O)O—, —S—, —SO—, —SO2—, —C(═S)—, —C(═NRy)—, or —N═N—,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 the group consisting of nitrogen, oxygen, and sulfur; or an optionally substituted 8-10 membered bivalent saturated, partially unsaturated, or aryl bicyclic ring having 0-5 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; andeach Ry is independently —H, or an optionally substituted group selected from the group consisting of: C1-6 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 the group consisting of nitrogen, oxygen, and sulfur,a 5-6 membered heteroaryl ring having 1-3 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur, and an8- to 10- membered aryl. 12. The catalyst of claim 1, wherein the at least one anionic metal carbonyl species is a compound of formula: [QdM′e(CO)w]y−, wherein: Q is a 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 a stable anionic metal carbonyl complex, andy is the charge of the anionic metal carbonyl species. 13. The catalyst of claim 12, wherein the at least one 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. 14. The catalyst of claim 12, wherein the at least one anionic metal carbonyl species is selected from the group consisting of: [Co(CO)4]−, [Ti(CO)6]2−, [V(CO)6]−, [Rh(CO)4]−, [Fe(CO)4]2−, [Ru(CO)4]2−, [Os(CO)4]2−, [Cr2(CO)10]2−, [Fe2(CO)8]2−, [Tc(CO)5]−, [Re(CO)5]−, and [Mn(CO)5]−. 15. The catalyst of claim 1, wherein the at least one anionic metal carbonyl species is [Co(CO)4]−. 16. The catalyst of claim 1, wherein the metal complex has a structure selected from the group consisting of: wherein: is selected from the group consisting of  wherein q is 3; andR1′, R2′, R3′, and R4′ are independently at each occurrence: hydrogen, halogen, —NO2, —CN, —SRy, —S(O)Ry, —S(O)2Ry, —NRyC(O)Ry, —OC(O)Ry, —CO2Ry, —NCO, —N3, —OR4, —OC(O)N(Ry)2, —N(Ry)2, —NRyC(O)Ry, or —NRyC(O)ORy; or an optionally substituted group selected from the group consisting of: C1-20 aliphatic;C1-20 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 the group consisting of nitrogen, oxygen, and sulfur; and4- to 7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur, orwherein two or more adjacent R1′, R2′, R3′, and R4′ groups are taken together to form an optionally substituted saturated, partially unsaturated, or aromatic 5- to 12-membered ring containing 0 to 4 heteroatoms. 17. A catalyst comprising a compound selected from the group consisting of: wherein M is aluminum or chromium. 18. A method comprising contacting ethylene oxide with carbon monoxide in the presence of a catalyst of claim 1, to provide a product comprising beta propiolactone, succinic anhydride, or polypropiolactone, or a mixture of any two or more of these. 19. The method of claim 18, wherein the product comprises beta propiolactone. 20. The method claim 18, wherein the product comprises polypropiolactone. 21. The catalyst of claim 1, wherein the linker is selected from the group consisting of: wherein each s is independently 0-6, t is 0-4, each * represents the site of attachment to the metal complex, and each # represents a site of attachment of Z+. 22. The catalyst of claim 1, wherein the metal complex has a structure selected from the group consisting of: wherein: is selected from the group consisting of 23. The catalyst of claim 1, wherein the metal complex has a structure selected from the group consisting of: wherein: is selected from the group consisting of R1′, R2′, R3′, and R4′ are independently at each occurrence: hydrogen, halogen, —NO2, —CN, —SRy, —S(O)Ry, —S(O)2Ry, —NRyC(O)Ry, —OC(O)Ry, —CO2Ry, —NCO, —N3, —OR4, —OC(O)N(Ry)2, —N(Ry)2, —NRyC(O)Ry, or —NRyC(O)ORy; or an optionally substituted group selected from the group consisting of: C1-20 aliphatic;C1-20 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 the group consisting of nitrogen, oxygen, and sulfur; and4- to 7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur, orwherein two or more adjacent R1′, R2′, R3′, and R4′ groups are taken together to form an optionally substituted saturated, partially unsaturated, or aromatic 5- to 12-membered ring containing 0 to 4 heteroatoms; andSo is an optionally present coordinated solvent molecule. 24. The catalyst of claim 1, wherein the metal complex has a structure selected from the group consisting of: 25. The catalyst of claim 1, wherein q is 3. 26. The catalyst of claim 1, wherein Z+comprises an atom selected from the group consisting of nitrogen and phosphorous. 27. The catalyst of claim 23, wherein the coordinated solvent molecule is an ether, an epoxide, DMSO, an amine, or other Lewis basic moiety. 28. A method comprising contacting ethylene oxide with carbon monoxide in the presence of a catalyst of claim 17, to provide a product comprising beta propiolactone, succinic anhydride, or polypropiolactone, or a mixture of any two or more of these. 29. The method of claim 28, wherein the product comprises beta propiolactone. 30. The method claim 28, wherein the product comprises polypropiolactone.