Carbon Dioxide Reduction to Methanol Catalyzed by Mn(I) PNP Pincer Complexes under Mild Reaction Conditions

Well-defined Mn­(I) hydrido carbonyl PNP pincer-type complexes were tested as efficient and selective nonprecious transition metal catalysts for the reduction of CO2 to MeOH in the presence of hydrosilanes. The choice of reaction temperature and type of silanes proved to be pivotal to achieve fast reactions and high selectivity to the methoxysilyl- vs silylformate derivatives in DMSO. The catalytic data are complemented by DFT calculations, highlighting a stepwise CO2 reduction mechanism centered on the Mn catalyst without metal-to-ligand cooperation.