An amide-based second coordination sphere promotes the dimer pathway of Mn-catalyzed CO₂-to-CO reduction at low...

The [fac-Mn(bpy)(CO)₃Br] complex is capable of catalyzing the electrochemical reduction of CO₂ to CO with high selectivity, moderate activity and large overpotential. Several attempts have been made to lower the overpotential and to enhance the catalytic activity of this complex by manipulating the second-coordination sphere of manganese and using relatively stronger acids to promote the protonation-first pathway. We report herein that the complex [fac-Mn(bpy-CONHMe)(CO)₃(MeCN)]⁺ ([1-MeCN]⁺; bpy-CONHMe = N-methyl-(2,2'-bipyridine)-6-carboxamide) as a pre-catalyst could catalyze the electrochemical reduction of CO₂ to CO with low overpotential and high activity and selectivity. Combined experimental and computational studies reveal that the amide NH group not only decreases the overpotential of the Mn catalyst by promoting the dimer and protonation-first pathways in the presence of H₂O but also enhances the CO₂ electroreduction activity by facilitating C-OH bond cleavage, making [1-MeCN]⁺ an efficient CO₂ reduction pre-catalyst at low overpotential.