Mediated Inner-Sphere Electron Transfer Induces Homogeneous Reduction of CO2 via Through-Space Electronic Conjugation

The electrocatalytic reduction of CO₂ is an appealing method for converting renewable energy sources into value-added chemical feedstocks. We report a co-electrocatalytic system for the reduction of CO₂ to CO comprised of a molecular Cr complex and dibenzothiophene-5,5-dioxide (DBTD) as a redox mediator which achieves high activity (TOF = 1.51-2.84 x 10⁵ s^–1) and quantitative selectivity. Under aprotic or protic conditions, DBTD produces a co-electrocatalytic response with <b>1</b> by coordinating <i>trans</i> to the site of CO₂ binding and mediating electron transfer from the electrode with quantitative efficiency for CO. This assembly is reliant on through-space electronic conjugation between the <i>π</i> frameworks of DBTD and the bpy fragment of the catalyst ligand, with contributions from dispersive interactions and weak sulfone coordination. The resulting interaction stabilizes a key intermediate in a new aprotic catalytic pathway and lowers the energy of the rate-determining transition state under protic conditions. To the best of our knowledge through-space electronic conjugation has not been explored in molecular electrocatalytic systems.<br>