Cobalt complexes with α-amino acid ligands catalyze the incorporation of CO₂ into cyclic carbonates

Arguably one of the largest research areas involving carbon dioxide (CO2) fixation is the coupling of CO2 to epoxides to form cyclic carbonates and polycarbonates. In this sense, there is an ever-increasing demand for the development of higher-performing catalytic systems that could counterbalance sustainability and energy efficiency in the production of cyclic carbonates. The use of abundant first-row transition metals combined with naturally occurring amino acids may be an ideal catalytic platform to fulfill this demand. Nevertheless, detailed information on the interactions between metal centers and natural products as catalysts in this transformation is lacking. Here a series of Co(III) amino acid catalysts operating in a binary system showed outstanding performance for the coupling reaction of epoxides and CO2. Nine new complexes of the type trans(N)-[Co(aa)2(bipy)]Cl (aa: ala, asp, lys, met, phe, pro, ser, tyr, and val) were used to explore the structure–activity relationship influenced by the complex outer coordination sphere, and its effect on the catalytic activity in the coupling reaction of CO2 and epoxides.