A Heterogeneous Manganese Catalyst for the Selective Hydrogenation of Nitroarenes

Catalytic hydrogenations of nitroarenes are fundamental processes in organic chemistry, allowing for atom-efficient and clean synthesis of valuable amines. Recently, earth-abundant metals have attracted considerable interest in this field. Surprisingly, despite more than a century of developments in heterogeneous catalysis, in the present study, we describe for the first time a specific manganese-based single-atom catalyst that allows the selective hydrogenation of various nitroarenes. The corresponding amines were obtained with a high selectivity, especially for nitrostyrene. In the hydrogenation process, the addition of H₂O was found to promote the activity of Mn₁-N-C/Al₂O₃. Mechanistic control experiments indicated that the heterolytic activation of hydrogen may be a contributing factor. This work provides an effective approach for the design of completely new Mn-based heterogeneous hydrogenation catalysts.