Non-Pincer Mn(I) Organometallics for the Selective Catalytic Hydrogenation of Nitriles to Primary Amines

We report herein selective catalytic hydrogenation of nitriles to primary amines with the use of the non-pincer Mn(I) compound fac-[(CO)(3)Mn{iPr(2)P(CH2)(2)PiPr(2)}(OTf)](2) as a catalytic precursor (3 mol %) in the presence of (KOBu)-Bu-t (10 mol %) and 2-BuOH as solvent. Benchmark benzonitrile and electron-rich aromatic and aliphatic nitriles were hydrogenated under rather mild conditions (7 bar, 90 degrees C, 15 min) to produce the corresponding amines in excellent to very good isolated yields (83-97%, six examples). Increasing the H-2 pressure and time (35 bar, 30 min) allowed for the production of (di)amines in excellent yields (94-98%, three examples) from electron-deficient aromatic nitriles and terephthalonitrile. Notably, adiponitrile was reduced to hexamethylenediamine in 53% isolated yield. Finally, mechanistic insights were performed and suggested unsaturated Mn-hydride species performing the elementary steps during catalytic turnover.