The catalysis of the reaction of carbon dioxide with epoxides (cyclohexene oxide or propylene oxide) using the (salen)(CrCl)-Cl-III complex as catalyst, where H(2)salen = N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexenediimine (1), to provide copolymer and cyclic carbonate has been investigated by in situ infrared spectroscopy. As previously demonstrated for the cyclohexene oxide/CO2 reaction in the presence of complex 1, coupling of propylene oxide and carbon dioxide was found to occur by way of a pathway first-order in catalyst concentration. Unlike the cyclohexene oxide/carbon dioxide reaction catalyzed by complex 1, which affords completely alternating copolymer and only small quantities of trans-cyclic cyclohexyl carbonate, under similar conditions propylene oxide/carbon dioxide produces mostly cyclic propylene carbonate. Comparative kinetic measurements were performed as a function of reaction temperature to assess the activation barrier for production of cyclic carbonates and polycarbonates for the two different classes of epoxides, i.e., alicyclic (cyclohexene oxide) and aliphatic (propylene oxide). As anticipated in both instances the unimolecular pathway for cyclic carbonate formation has a larger energy of activation than the bimolecular enchainment pathway. That is, the energies of activation determined for cyclic propylene carbonate and poly(propylene carbonate) formation were 100.5 and 67.6 kJ(.)mol(-1), respectively, compared to the corresponding values for cyclic cyclohexyl carbonate and poly(cyclohexylene carbonate) production of 133 and 46.9 kJ(.)mol(-1). The small energy difference in the two concurrent reactions for the propylene oxide/CO2 process (33 kJ(.)mol(-1)) accounts for the large quantity of cyclic carbonate produced at elevated temperatures in this instance.