The mechanism of the copolymerization of cyclohexene oxide and carbon dioxide to afford poly(cyclohexylene)carbonate catalyzed by (salen)CrN3 (H(2)salen = N,N,'-bis(3,5-di-tert-butylsalicylidene)-1,2ethylene-diimine) in the presence of a broad range of cocatalysts has been studied. We have previously established the rate of copolymer formation to be very sensitive to both the electron-donating ability of the salen ligand and the [cocatalyst], where N-heterocyclic amines, phosphines, and ionic salts were effective cocatalysts. Significant increases in the rate of copolymerization have been achieved with turnover frequencies of similar to 1200 h(-1), thereby making these catalyst systems some of the most active and robust thus far uncovered. Herein we offer a detailed explanation of the role of the cocatalyst in the copolymerization Of CO2 and cyclohexene oxide catalyzed by chromium salen derivatives. A salient feature of the N-heterocyclic amine- or phosphine-cocatalyzed processes is the presence of an initiation period prior to reaching the maximum rate of copolymerization. Importantly, this is not observed for comparable processes involving ionic salts as cocatalysts, e.g., PPN+X-. In these latter cases the copolymerization reaction exhibits ideal kinetic behavior and is proposed to proceed via a reaction pathway involving anionic six-coordinate (salen)Cr(N-3)X-derivatives. By way of infrared and P-31 NMR spectroscopic studies, coupled with in situ kinetic monitoring of the reactions, a mechanism of copolymerization is proposed where the neutral cocatalysts react with CO2 and/or epoxide to produce inner salts or zwitterions which behave in a manner similar to that of ionic salts.