Coupling reaction of carbon dioxide and epoxides efficiently catalyzed by one-component aluminum–salen complex under solvent-free conditions

Abstract

Four novel bifunctional aluminum–salen complexes (2a, 2b, 2c, and 2d) containing both Lewis acidic metal center and Lewis base quaternary phosphonium salt sites within one molecule and an aluminum–salen complex with a neutral tert-butyl group (2f) for comparison were synthesized and characterized by UV–vis, IR, 1H, 13C, 27Al NMR spectroscopy and Elemental analysis (EA). Their catalytic efficiencies as single-component catalysts toward the coupling reaction of carbon dioxide and propylene oxide were evaluated. These complexes exhibit catalytic activity in the order 2d>2a>2b>2c≫2f. 27Al NMR spectra reveal the existence of five- and six-coordinated metal centers in the aluminum–salen complexes bearing a quaternary phosphonium salt group, whereas only five-coordinate aluminum species were found in the aluminum–salen complex with a neutral tert-butyl group. This indicates the importance of the six-coordinate aluminum center in enhancing the catalytic activity as well as an intramolecular cooperative effect in bifunctional aluminum–salen complexes 2a–d. The effects of reaction variables on the catalytic performance were investigated in detail. These new catalysts are highly stable to moisture and air and robust to impurities in the coupling reaction.