Zinc versus Magnesium: Orthogonal Catalyst Reactivity in Selective Polymerizations of Epoxides, Bio‐derived Anhydrides and Carbon Dioxide

Developing selective polymerizations from complex monomer mixtures is an important challenge. Here, dinuclear catalysts allow selective polymerization from mixtures of sterically hindered tricyclic anhydrides, carbon dioxide and epoxides to yield well‐controlled copoly(ester‐carbonates). Surprisingly, two very similar homogeneous catalysts differing only in the central metal, zinc versus magnesium, show very high but diametrically opposite monomer selectivity. The selectivity is attributed to different polymerization kinetics and to steric factors associated with the anhydrides.