Metal−Halide Bond Photoactivation from a Pt^III−Au^II Complex

The d8···d10 heterobimetallic [PtIIAuI(dppm)2PhCl]PF6 (1) complex (dppm = bis(diphenylphosphino)methane) is oxidized by PhICl2 to give the d7−d9 [PtIIIAuII(dppm)2PhCl3]PF6 (2) complex containing a PtIII−AuII bond. Facile M−X bond activation is achieved by irradiation of CH3CN solutions of 2 with visible light in the presence of 2,3-dimethyl-1,3-butadiene, inducing a two-electron reduction to regenerate 1.