Unmasking the Ligand Effect in Manganese-Catalyzed Hydrogenation: Mechanistic Insight and Catalytic Application

Manganese-catalyzed hydrogenation reactions have attracted broad interest since the first report in 2016. Among the reported catalytic systems, Mn catalysts supported by tridentate PNP- and NNP-pincer ligands have most commonly been used. For example, a number of PNP-Mn pincer catalysts have been reported for the hydrogenation of aldehydes, aldimines, ketones, nitriles, and esters. Furthermore, various NNP-Mn pincer catalysts have been shown to be active in the hydrogenation of less-reactive substrates such as amides, carbonates, carbamates, and urea derivations. These observations indicated that Mn catalysts supported by NNP-pincer ligands exhibit higher reactivity in hydrogenation reactions than their PNP counterparts. Such a ligand effect in Mn-catalyzed hydrogenation reactions has yet to be confirmed. Herein, we investigated the origin and applicability of this ligand effect. A combination of experimental and theoretical investigations showed that NNP-pincer ligands on the Mn complexes were more elect...