A Highly Active N‐Heterocyclic Carbene Manganese(I) Complex for Selective Electrocatalytic CO2 Reduction to CO

Abstract

We report here the first purely organometallic fac‐[MnI(CO)3(bis‐MeNHC)Br] complex with unprecedented activity for the selective electrocatalytic reduction of CO2 to CO, exceeding 100 turnovers with excellent faradaic yields (ηCO≈95 %) in anhydrous CH3CN. Under the same conditions, a maximum turnover frequency (TOFmax) of 2100 s−1 was measured by cyclic voltammetry, which clearly exceeds the values reported for other manganese‐based catalysts. Moreover, the addition of water leads to the highest TOFmax value (ca. 320 000 s−1) ever reported for a manganese‐based catalyst. A MnI tetracarbonyl intermediate was detected under catalytic conditions for the first time.