Primary photochemical processes for PtCl62− complex in acetonitrile solutions

Abstract

Photosolvation of hexachloroplatinate(IV) in acetonitrile with the formation of the PtIVCl5(CH3CN)− complex was studied in the time range from hundreds of femtoseconds to seconds. The primary Pt(III) intermediate was recorded and interpreted as the primary Adamson radical pair [PtIIICl52‐(C4v)⋯Clradical dot], which then accepts an electron from a solvent molecule. Two successive Pt(III) intermediates recorded in time range from microseconds to tens of milliseconds were interpreted as PtIIICl52−(C4V) and PtIIICl4− complexes. PtIIICl4− was proposed to be a chain carrier in the chain photosolvation process. Dependencies of quantum yield of photosolvation on the initial complex concentration and excited light intensity were fitted in the framework of the proposed chain mechanism. Rate constants of the reactions of intermediates were determined.