Aryl halides are important chemical components in organic syntheses. Herein, we report visible-light-induced, single nickel-catalyzed halogen exchange of aromatic halides with the corresponding halide salts under mild conditions. Varieties of aryl iodides, bromides, and chlorides can smoothly undergo aromatic Finkelstein or retro-Finkelstein reactions with good functional group tolerance. Experimentally, mechanistic studies showed that excited-state NiII complexes for facile reductive elimination to form carbon–halide bonds were involved in the process of Finkelstein and retro-Finkelstein reactions.

Herein, we report visible light‐promoted single nickel catalysis for diverse carbon–heteroatom couplings under mild conditions. This mild, general, and robust method to couple diverse nitrogen, oxygen, and sulfur nucleophiles with aryl(heteroaryl)/alkenyl iodides/bromides exhibits a wide functional group tolerance and is applicable to late‐stage modification of pharmaceuticals and natural products. On the base of preliminary mechanistic studies, a NiI/NiIII cycle via the generation of active NiI complexes that appear from homolysis of NiII−I rather than NiII−aryl bond was tentatively proposed.

Herein, we report light-promoted photo/hydrogen atom transfer dual catalysis for arylsilylation of alkenes via the radical−radical cross-coupling with diverse hydrosilanes, which provides a simple and efficient method to prepare various organosilicon compounds with a wide range of substrate scope and good functional group tolerance under transition-metal-and chemical-oxidant-free conditions. Furthermore, the arylsilylation of alkenes can also proceed via the possible electron donor− acceptor complex under exogenous photocatalyst-free conditions.