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The present disclosure is directed, in part, to methods of synthesizing a poly(ethylene carbonate) polymer from the reaction of ethylene oxide (EO) and carbon dioxide (CO2) in the presence of a metal complex. The present disclosure also provides novel metal complexes. In one aspect, the metal comple

The present disclosure is directed, in part, to methods of synthesizing a poly(ethylene carbonate) polymer from the reaction of ethylene oxide (EO) and carbon dioxide (CO2) in the presence of a metal complex. The present disclosure also provides novel metal complexes. In one aspect, the metal complex is of the formula (I), wherein R1, R2, R3, M, X and Ring A are as defined herein.

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1. A method of synthesizing a poly(ethylene carbonate) polymer, wherein the polymer is made up of Y, and optionally Z, the percentage of Y is greater than the percentage of Z, and the polymer has greater than 95% of Y, the method comprising reacting ethylene oxide and carbon dioxide in the presence

1. A method of synthesizing a poly(ethylene carbonate) polymer, wherein the polymer is made up of Y, and optionally Z, the percentage of Y is greater than the percentage of Z, and the polymer has greater than 95% of Y, the method comprising reacting ethylene oxide and carbon dioxide in the presence of a metal complex, wherein the metal complex is of the formula: wherein:M is a metal selected from zinc, cobalt, chromium, aluminum, titanium, ruthenium or manganese;X is absent or is a nucleophilic ligand;each instance of R3 is, independently, selected from hydrogen, halogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, and optionally substituted heteroaryl;R7 and R9 are, independently, selected from hydrogen, halogen, —ORc, —OC(═O)Rc, —OC(═O)ORc, —OC(═O)N(Rd)2, —OSO2Rd, —C(═O)ORc, —C(═O)N(Rd)2, —CN, —CNO, —NCO, —N3, —NO2, —N(Rd)2, —N(Rd)C(═O)ORc, —N(Rd)C(═O)Rc, —N(Rd)SO2Rd, —SO2Rd, —SORd, —SO2N(Rd)2, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, optionally substituted heteroaryl, wherein each instance of Rc is, independently, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, optionally substituted heteroaryl, and each instance of Rd is, independently, hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, optionally substituted heteroaryl;wherein the A value of at least one of R7 and R9 is greater than the A-value of tert-butyl; andRing A forms an optionally substituted 5- to 6-membered ring. 2. The method according to claim 1, wherein the metal complex is of the formula: 3. The method according to claim 1, wherein the metal complex is of the formula: 4. The method according to claim 1, wherein R7 is an optionally substituted C1-10 aliphatic group. 5. The method according to claim 1, wherein R7 is an optionally substituted C1-10 alkyl group. 6. The method according to claim 1, wherein R7 is selected from methyl, trichloromethyl, trifluoromethyl, ethyl, n-propyl, isopropyl, t-butyl, sec-butyl, iso-butyl, n-pentyl, neopentyl, amyl, trityl, adamantyl, thexyl, benzyl and cumyl. 7. The method according to claim 1, wherein R9 is an optionally substituted C1-10 aliphatic group. 8. The method according to claim 1, wherein R9 is an optionally substituted C1-10 alkyl group. 9. The method according to claim 1, wherein R9 is selected from methyl, trichloromethyl, trifluoromethyl, ethyl, n-propyl, isopropyl, t-butyl, sec-butyl, iso-butyl, n-pentyl, neopentyl, amyl, trityl, adamantyl, thexyl, benzyl and cumyl. 10. The method according to claim 1, wherein the A-value of R9 is between about 0 to about 2.5 kcal/mol. 11. The method according to claim 1, wherein the metal complex is selected from any of the following formulae: 12. The method according to claim 1, wherein M is cobalt. 13. The method according to claim 1, wherein X is absent or is selected from the group consisting of: —ORx, —SRx, —O(C═O)Rx, —O(C═O)ORx, —O(C═O)N(Rx)2, —N(Rx)(C═O)Rx, —NC, —CN, halo, —N3, —O(SO2)Rx and —OPRx, wherein each Rx is, independently, selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl and optionally substituted heteroaryl. 14. The method according to claim 1, wherein X is —O(C═O)C6F5, —O(C═O)C6H5, —O(C═O)CF3, —O(C═O)CH3, —NC, —CN, —N3, —Cl, or —Br. 15. The method according to claim 14, wherein X is —O(C═O)C6F5. 16. The method according to claim 1, wherein the reaction further comprises a co-catalyst, wherein the co-catalyst is a salt. 17. The method according to claim 16, wherein the salt is an ammonium, phosphonium, or arsonium salt. 18. The method according to claim 17, wherein the ammonium salt is (n-Bu)4NCl, (n-Bu)4NBr, (n-Bu)4NN3, [PPN]Cl, [PPN]Br, or [PPN]N3. 19. The method according to claim 1, wherein the polymer has greater than about 99% of Y. 20. The method according to claim 19, wherein the polymer is 100% of Y and 0% of Z. 21. The method according to claim 1, wherein the polymer is of the formula: P is an integer of between about 10,000 and about 15,000, inclusive; andF and G are, independently, suitable terminating groups. 22. A method of synthesizing a poly(ethylene carbonate) polymer, comprising a step of reacting ethylene oxide with carbon dioxide in the presence of a cobalt complex, wherein the cobalt complex is any one of the formulae: wherein X is absent or is a nucleophilic ligand; andwherein the polymer has greater than 95% carbonate linkages. 23. A metal complex of the formula: wherein:M is a metal selected from zinc, cobalt, chromium, aluminum, titanium, ruthenium or manganese;X is absent or is a nucleophilic ligand;R7 and R9 are, independently, selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, optionally substituted heteroaryl;wherein the A value of at least one of R7 and R9 is greater than the A-value of tert-butyl; andR4A, R4B, R5A, R5B, and R6A, R6B are, independently, selected from hydrogen, halogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, optionally substituted heteroaryl, and/or, R4A and R4B, and/or R5A and R5B, and/or and R6A and R6B are optionally joined to form an oxo (═O) group, an oxime (═NORa) group, an imine (═NN(Ra)2) group, an alkenyl (═C(Rb)2) group, and/or a 3- to 6-membered spirocyclic ring, wherein each instance of Ra and Rb is, independently, hydrogen or optionally substituted aliphatic, wherein optionally two Ra groups or two Rb groups are joined to form a 3- to 6-membered ring. 24. The method of claim 1, wherein R7 and R9 are the same. 25. The method of claim 1, wherein R7 and R9 are different.