Bimetallic Cooperativity and Hydrogen Bonding Allow Efficient Reduction of CO2

Abstract Reducing CO 2 selectively to one of the several C1 products is challenging, as the thermodynamic reduction potentials for the different n e − / n H + reductions of CO 2 are similar and so is the reduction potential for H + reduction. Recently, Halime, Aukauloo, and co‐workers have taken inspiration from the active site of nickel CO dehydrogenase (Ni‐CODH) to design bimetallic iron porphyrins bridged by a urea moiety. These complexes show fast and selective reduction of CO 2 to CO and the results suggest a Ni‐CODH type mechanism at play where one of the two metals binds and reduces the CO 2 while the other stabilizes the reduced species by forming a bridged complex, facilitating the C−O bond cleavage.