Two-Coordinated Au(I) Complex Photoredoxcatalyst: Highly Efficient Catalysis in C-C Cross-coupling Reactions and the Underlying Mechanism

Abstract

Photocatalysis provides a versatile approach to redox activation of various organic substrates for synthetic applications. To broaden the scope of photoredox catalysis, developing catalysts with strong photoredox power is imperative. Photoredox catalysts with excited-state properties that include cathodic oxidation potentials and long lifetimes are particularly demanded. In this research, we demonstrate the high-efficiency catalytic utility of two-coordinated Au(I) complex photocatalysts that exhibit an exclusive ligand-to-ligand charge-transfer (LLCT) transition in C-C cross-coupling reactions between N-heterocycles and (hetero)aryl halides, including redox-resistant (hetero)aryl chlorides. Our photocatalysis system can steer reactions under visible-light irradiation at a catalyst loading as low as 0.1 mol% and exhibits a broad substrate scope with high chemo- and regioselectivity. Our mechanistic investigations provide direct spectroscopic evidence for each step in the catalysis cycle and demonstrate that the LLCT-active Au(I) complex catalysts offer several benefits, including strong visible-light absorption, a 207 ns-long excited-state lifetime without short-lived components, and a 91% yield in the production of free-radical intermediates. Given the wide structural versatility of the proposed catalysts, we envision that our research will provide useful insights into the future utilization of the LLCT-active Au(I) complex for organic transformations.