A series of zinc phenoxides of the general formula (2,6-R2C6H3O)(2)Zn(base)(2) [R = Ph, Bu-t, Pr-i, base = Et2O, THF, or propylene carbonate] and (2,4,6-Me3C6H2O)(2)Zn(pyridine)(2) have been synthesized and characterized in the solid state by X-ray crystallography. All complexes crystallized as four-coordinate monomers with highly distorted tetrahedral geometry about the zinc center. The angles between the two sterically encumbering phenoxide ligands were found to be significantly more obtuse than the corresponding angles between the two smaller neutral base ligands, having average values of 140 degrees and 95 degrees, respectively. In a noninteracting solvent such as benzene or methylene chloride at ambient temperature, the ancillary base ligands are extensively dissociated from the zinc center, with the degree of dissociation being dependent on the base as well as the substituents on the phenolate ligands. That is, stronger ligand binding was found in zinc centers containing electron-donating tert-butyl substituents as opposed to electron-withdrawing phenyl substituents. In all instances, the order bf ligand binding was pyridine > THF > epoxides. These bis(phenoxide) derivatives of zinc were shown to be very effective catalysts for the copolymerization of cyclohexene oxide and CO2 in the absence of strongly coordinating solvents, to afford high-molecular-weight polycarbonate (M-w ranging from 45 x 10(3) to 173 x 10(3) Da) with low levels of polyether linkages. However, under similar conditions, these zinc complexes only coupled propylene oxide and CO2 to produce cyclic propylene carbonate. Nevertheless, these bis (phenoxide) derivatives of zinc were competent at terpolymerization of cyclohexene oxide/propylene oxide/CO2 with little cyclic propylene carbonate formation at low propylene oxide loadings. While CO2 showed no reactivity with the sterically encumbered zinc bis(phenoxides), e.g., (2,6-di-tert-butylphenoxide)(2)Zn(pyridine)(2), it rapidly inserted into one of the Zn-O bonds of the less crowded (2,4,6-trimethylphenoxide)(2)Zn(pyridine)(2) to provide the corresponding aryl carbonate zinc derivative. At the same time, both sterically hindered and sterically nonhindered phenoxide derivatives of zinc served to ring-open epoxide, i.e., were effective catalysts for the homopolymerization of epoxide to polyethers. The relevance of these reactivity patterns to the initiation step of the copolymerization process involving these monomeric zinc complexes is discussed.