Bimetallic Nickel Complexes as Effective and Versatile Catalysts for Copolymerization of Epoxides with Carbon Dioxide or Phthalic Anhydride: Catalysis and Kinetics.

This study reported three novel structurally well-characterized dihalide dinuclear nickel complexes containing benzotriazole-based 1,3-diamine-linked bisphenolate ligands, which were high-performance catalysts for ring-opening copolymerization (ROCOP) of cyclohexene oxide (CHO) and carbon dioxide (CO2). The dinickel diiodo 3 was shown to catalyze CO2 copolymerization of CHO with high activity (turnover frequency up to 2250 h-1), excellent selectivity (>99% polycarbonates, >99% carbonate repeated units), and good molecular weight controllability. Apart from CO2/CHO copolymerization, the most active complex 3 was found to effectively catalyze ROCOP of CHO with phthalic anhydride (PA). Not only has the controllable manner of 3 for PA/CHO copolymerization been proven but also a broad substrate scope for PA copolymerization of epoxides by the same complex has been achieved. Diverse terminal or internal epoxides were demonstrated to copolymerize PA by 3, producing the corresponding semiaromatic polyesters with good activity and excellent product selectivity. Kinetic studies for CHO copolymerization of CO2 or PA mediated by 3 were systematically investigated. For kinetics of PA/CHO copolymerization, it allowed us to propose the rate equation of -d[CHO]/dt = kp[3]1[PA]0[CHO]1, and such catalysis displayed a first-order dependence on both dinickel complex and CHO concentrations as well as a zero order for PA. This work offers a bimetallic dihalide nickel complex as an efficient and versatile catalyst for two different types of copolymerization catalysis.