Manganese N‑Heterocyclic Carbene Pincers for the Electrocatalytic Reduction of Carbon Dioxide

We report the synthesis, characterization, and catalytic CO2 reduction activity of two LMn­(CO)3Br complexes with carbene-pyridine-carbene pincer ligands, [MnCNCMe]Br 1 and [MnCNCBn]Br (Bn = benzyl) 2. X-ray crystallography reveals an octahedral coordination environment with an outer sphere Br anion for 1. Catalyst 2 performs the reduction of CO2 to CO at 100 mV more positive potential with similar current densities as 1. We hypothesize the bulkier benzyl arms on the pincer hinder formation of a dimer. They also alter the wingtip electronics, enabling operation at a lower overpotential. We use normal pulse voltammetry and diffusion ordered spectroscopy to quantify a 1e– reduction per manganese center at the catalytic onset. We now show turnover even in the absence of added protons..