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

We report here the first purely organometallic fac-[MnI (CO)3 (bis-Me NHC)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 CH3 CN. 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.