Mechanism of Photoredox-Initiated C–C and C–N Bond Formation by Arylation of IPrAu(I)–CF₃ and IPrAu(I)–Succinimide

Herein, we report on the photoredox-initiated gold-mediated C­(sp2)–CF3 and C­(sp2)–N coupling reactions. By adopting gold as a platform for probing metallaphotoredox catalysis, we demonstrate that cationic gold­(III) complexes are the key intermediates of the C–C and C–N coupling reactions. The high-valent gold­(III) intermediates are accessed by virtue of photoredox catalysis through a radical chain process. In addition, the bond-forming step of the coupling reactions is the reductive elimination from cationic gold­(III) intermediates, which is supported by isolation and crystallographic characterization of key Au­(III) intermediates.