Hydrogenation and electrocatalytic reduction of carbon dioxide to formate with a single Co catalyst

A cobalt( i ) complex is shown to be capable of both electrocatalytic reduction and hydrogenation of CO 2 to formate. Several proposed intermediates are characterized and thus form the basis for a proposed mechanism that allows for the dual reactivity: reduction of CO 2 via H 2 addition, and H + /e − equivalents. The work makes use of a novel tris(phosphino) ligand. When a pendent amine is attached to the ligand, no change in catalytic reactivity is observed. A cobalt( i ) complex is shown to be capable of both electrocatalytic reduction and hydrogenation of CO 2 to formate.