A Highly Active N‐Heterocyclic Carbene Manganese(I) Complex for Selective Electrocatalytic CO(2) Reduction to CO

We report here the first purely organometallic fac‐[Mn(I)(CO)(3)(bis‐(Me)NHC)Br] complex with unprecedented activity for the selective electrocatalytic reduction of CO(2) to CO, exceeding 100 turnovers with excellent faradaic yields (η (CO)≈95 %) in anhydrous CH(3)CN. Under the same conditions, a maximum turnover frequency (TOF(max)) 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 TOF(max) value (ca. 320 000 s(−1)) ever reported for a manganese‐based catalyst. A Mn(I) tetracarbonyl intermediate was detected under catalytic conditions for the first time.