Co-electrocatalytic CO₂ reduction mediated by a dibenzophosphole oxide and a chromium complex

We report a co-electrocatalytic system for the selective reduction of CO₂ to CO, comprised of a previously reported molecular Cr complex and 5-phenylbenzo[b]phosphindole-5-oxide (PhBPO) as a redox mediator. Under protic conditions, the co-electrocatalytic system attains a turnover frequency (TOF) of 15 s^-1 and quantitative selectivity for CO. It is proposed that PhBPO interacts with the Cr-based catalyst, coordinating in an axial position trans to an intermediate hydroxycarbonyl species, M-CO₂H, mediating electron transfer to the catalyst and lowering the barrier for C-OH bond cleavage.