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

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