The reactions of zinc halides with 2,6-di-methoxypyridine or 3-trifluoromethylpyridine in dichloromethane have led to the formation of quite different complexes. Specifically, reactions involving pyridine containing electron donating methoxy substituents have provided salts of the type [Zn(2,6-dimethoxypyridine)(4)][Zn2X6], as revealed by elemental analysis and X-ray crystallography. On the other hand, simple bis-pyridine adducts of zinc halides were isolated from the reactions involving the pyridine ligand with electron withdrawing substituents and characterized by X-ray crystallography, for example, Zn (3-trifluoromethylpyridine)(2)Br-2. These zinc complexes were shown to be catalytically active for the coupling of carbon dioxide and epoxides to provide high molecular weight polycarbonates and cyclic carbonates, with the order of reactivity being Cl greater than or equal to Br > 1, and 2,6-di-methoxypyridine > 3-trifluoromethylpyridine. Polycarbonate production from carbon dioxide and cyclohexene oxide was shown to be first-order in both metal precursor complex and cyclohexene oxide, as monitored by in situ infrared spectroscopy at 80 degreesC and 55 bar pressure. For reactions carried out in CO2 Swollen epoxide solutions in the absence of added quantities of pyridine, the copolymer produced contained significant polyether linkages. Alternatively, reactions performed in the presence of excess pyridine or in hydrocarbon solvent, although slower in rate, afforded completely alternating copolymers. For comparative purposes, zinc chloride was a very effective homopolymerization catalyst for polyethers. Additionally, zinc chloride afforded copolymers with 60% carbonate linkages in the presence of high carbon dioxide pressures. In the case of cyclohexene oxide, the copolymer back-biting reaction led exclusively to the production of the trans cyclic carbonate as shown by infrared spectroscopy in v(C=O) region and X-ray crystallography. The unique feature of these catalyst systems is their simplicity.