Nickel(IV)-Catalyzed C–H Trifluoromethylation of (Hetero)arenes

This Article describes the development of a stable Ni^IV complex that mediates C(sp²)–H trifluoromethylation reactions. This reactivity is first demonstrated stoichiometrically and then successfully translated to a Ni^IV-catalyzed C–H trifluoromethylation of electron-rich arene and heteroarene substrates. Both experimental and computational mechanistic studies support a radical chain pathway involving Ni^IV, Ni^III, and Ni^II intermediates.