Carbon Dioxide Hydrogenation to Formate Catalyzed by a Neutral, Coordinatively Saturated Tris‐Carbonyl Mn(I)‐PNP Pincer‐Type Complex.

CO2 catalytic hydrogenation to formate was achieved (TONmax=ca. 3800) in the presence of the neutral, halide‐free, coordinatively saturated tris(carbonyl) manganese pincer‐type complex [Mn(PNP)(CO)3], bearing a diarylamido pincer‐type PNP ligand, using DBU as base and LiOTf as Lewis acid additive, under mild reaction conditions (60 bar, 80 °C). DFT calculations suggest that the precatalyst activation key step occurs by intermolecular, base assisted dihydrogen heterolytic splitting rather than by the expected ligand‐assisted intramolecular MLC‐type mechanism. [ABSTRACT FROM AUTHOR]