Cobalt Complex with Redox‐Active Imino Bipyridyl Ligand for Electrocatalytic Reduction of Carbon Dioxide to Formate

An imino bipyridine cobalt(II) complex was developed for the electrocatalytic reduction of CO2 to formate in acetonitrile with a faradaic efficiency of approximately 80 %. For comparison, a symmetric bis‐imino pyridine complex showed lower catalytic activity because of less conjugation in the system. Cyclic voltammetry, electron paramagnetic resonance and IR spectroscopy studies provided mechanistic details and the structures of the key intermediates. DFT calculations confirmed the role of large π‐conjugated groups for stabilizing key intermediates through electronic conjugation.