Mechanistic insights into the visible-light-driven O-arylation of carboxylic acids catalyzed by xanthine-based nickel...

We present a photocatalytic protocol for the O-arylation of carboxylic acids using nickel complexes bearing C8-pyridyl xanthines. Our studies suggest that the underlying mechanism operates independently of external photosensitizers. Stoichiometric experiments and crystallographic studies characterize the catalytically relevant Ni complexes. Spectroscopic and computational investigations propose a thermally controlled Ni(i)/Ni(iii) cycle followed by a photochemical regeneration of Ni(i) species. Furthermore, the pathways leading to the hydrodehalogenation of aryl halides, the comproportionation of Ni(i) and Ni(iii) species, the dimerization of Ni(i) intermediates and the influence of the counter ion on the cross-coupling reaction are unveiled. These investigations offer a comprehensive mechanistic understanding of the photocatalytic cross-coupling reaction catalyzed by a single Ni species and highlight key aspects of nickel-catalyzed metallaphotoredox reactions.