Cationic tetranuclear macrocyclic CaCo₃ complexes as highly active catalysts for alternating copolymerization of...

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.