Photochemical Oxygen‐Atom‐Transfer Reactivity of Platinum(II) Peroxycarbonates

Peroxycarbonate (CO 4 2– ) is implicated in various biological, catalytic, and energy storage processes – despite the capability of transition metals to guide the reactivity of this unstable intermediate toward productive ends, the coordination chemistry of metal–peroxycarbonate complexes, M(CO 4 ), remains poorly understood. Herein, we describe the synthesis, isolation, and structural characterization of two platinum(II) peroxycarbonate complexes Pt(PPh 3 ) 2 (CO 4 ) ( 1 ) and Pt(dppe)(CO 4 ) ( 2 ) (dppe = 1,2‐bis(diphenylphosphino)ethane). Whereas the complexes are thermally stable, they react by oxygen‐atom transfer (OAT) when irradiated with visible light. This photoreactivity was investigated using NMR and FT‐IR photolysis to identify structures of reaction intermediates and photoproducts, together with kinetic analyses, which establish unimolecular OAT from the CO 4 2− ligand to the bound phosphine. In addition to providing rare examples of structurally characterized M(CO 4 ) complexes, this work is the first demonstration of photochemical reactivity in a peroxycarbonate complex.