Syntheses, Characterization, and Application of Tridentate Phenoxyimino-Phenoxy Aluminum Complexes for the Coupling of Terminal Epoxide with CO2: From Binary System to Single Component Catalyst

Abstract

A series of binuclear aluminum complexes 1–3 supported by tridentate phenoxyimino-phenoxy ligands was synthesized and used as catalysts for the coupling reaction of terminal epoxide with carbon dioxide. The aluminum complex 1, which is catalytically inactive toward the coupling of epoxide with CO2 by itself, shows moderate activity in the presence of excess nucleophiles or organic bases at high temperature. In sharp contrast to complex 1, bifunctional complexes 2 and 3, which incorporate tertiary amine groups as the built-in nucleophile, are able to efficiently transform terminal epoxide with CO2 to corresponding cyclic carbonates as a sole product by themselves at 100 °C. The number of amine groups on the ligand skeleton and the reaction temperature exert a great influence on the catalytic activity. The bifunctional complexes 2 and 3 are also active at low carbon dioxide pressure such as 2 atm or atmospheric CO2 pressure. Kinetic studies of the coupling reactions of chloropropylene oxide/CO2 and styrene oxide/CO2 using bifunctional catalysts under atmospheric pressure of CO2 demonstrate that the coupling reaction has a first-order dependence on the concentration of the epoxide.