A Mn-complex bearing redox-active phenalenyl (PLY) ligand can undergo three successive reductions to generate an active catalyst consisting of ligand-centered radical, which plays the key role in activating inert PMHS for silylative dehydration of amide to nitrile under ambient conditions, following a radical pathway.

Abstract

A redox-active phenalenyl ligand coordinated Mn(III)-complex can be reduced chemically to generate an active catalyst containing a ligand-centered radical. This chemically reduced Mn-catalyst shows excellent catalytic reactivity for silylative dehydration of a wide range of primary amides (including late-stage diversification of various bio-active molecules) to synthesize nitriles using an inert and inexpensive silane, polymethylhydrosiloxane (PMHS), under mild conditions. Control experiments suggest a radical pathway for the present catalytic reaction, initiated by the ligand-centered radical.