Chem Sci. 2023 Jul 12;14(31):8262-8268. doi: 10.1039/d3sc00974b. eCollection 2023 Aug 9.
We found that a cationic hetero tetranuclear complex including a calcium and three cobalts exhibited high catalytic activity toward alternating copolymerization of propylene oxide (PO) and carbon dioxide (CO2). The tertiary anilinium salt [PhNMe2H][B(C6F5)4] was the best additive to generate the cationic species while maintaining polymer selectivity and carbonate linkage, even under 1.0 MPa CO2. Density functional theory calculations clarified that the reaction pathway mediated by the cationic complex is more favorable than that mediated by the neutral complex by 1.0 kcal mol-1. We further found that the flexible ligand exchange between Ca and Co ions is important for the alternating copolymerization to proceed smoothly.