A bioinspired molybdenum-copper molecular catalyst for CO₂ electroreduction

Non-noble metal molecular catalysts mediating the electrocatalytic reduction of carbon dioxide are still scarce. This work reports the electrochemical reduction of CO₂ to formate catalyzed by the bimetallic complex [(bdt)Mo^VI(O)S₂Cu^ICN]^2- (bdt = benzenedithiolate), a mimic of the active site of the Mo-Cu carbon monoxide dehydrogenase enzyme (CODH2). Infrared spectroelectrochemical (IR-SEC) studies coupled with density functional theory (DFT) computations revealed that the complex is only a pre-catalyst, the active catalyst being generated upon reduction in the presence of CO₂. We found that the two-electron reduction of [(bdt)Mo^VI(O)S₂Cu^ICN]^2- triggers the transfer of the oxo moiety to CO₂ forming CO₃ ^2- and the complex [(bdt)Mo^IVS₂Cu^ICN]^2- and that a further one-electron reduction is needed to generate the active catalyst. Its protonation yields a reactive Mo^VH hydride intermediate which reacts with CO₂ to produce formate. These findings are particularly relevant to the design of catalysts from metal oxo precursors.