Mechanistic Studies of Cyclohexene Oxide/CO₂ Copolymerization by a Chromium(III) Pyridylamine-Bis(Phenolate) Complex

Chromium(III) chlorido amine-bis(phenolate) complexes paired with nucleophilic co-catalysts are a promising family of catalysts for the copolymerization of CO₂ and epoxides to selectively produce polycarbonates with a very high degree of carbonate linkages. Single-component catalyst systems can be prepared, where the neutral nucleophile, 4-dimethylaminopyridine (DMAP), is coordinated to the metal site to provide a stable octahedral Cr^III complex. These complexes possess the potential for both anionic (from the chlorido ligand) or neutral (DMAP) nucleophilic epoxide ring-opening during the proposed rate-determining initiation step. Concentration effect studies support a first-order dependence of the polymerization rate on the concentration of single-component catalyst. End-group analysis of polycarbonates by MALDI-TOF MS indicate the presence of predominantly DMAP-initiated chains as well as the occurrence of chain-transfer events resulting in ether linkages, likely from the presence of cyclohexene diol formed by the reaction of cyclohexene oxide and adventitious water.