Abstract
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.