Photoinduced Trifluoromethylation of Arenes and Heteroarenes Catalyzed by High‐Valent Nickel Complexes

We describe a series of air-stable NiIII complexes supported by simple, robust naphthyridine-based ligand. Access to the high-valent oxidation state is enabled CF3 ligands on nickel, while naphthyridine exhibits either monodentate or bidentate coordination mode that depends and sterics, enables facile aerobic NiII NiIII. These act as efficient catalysts for photoinduced C(sp2)−H bond trifluoromethylation reactions (hetero)arenes using versatile synthetic protocols. This blue LED light-mediated catalytic protocol proceeds via radical pathway demonstrates potential in late-stage functionalization drug analogs.