Add time:08/06/2019         Source:sciencedirect.com

A study of the photoaquation of hexachloroplatinate(IV) to pentachloroaquoplatinate(IV) in 1F perchloric acid medium has revealed that the overall quantum yield for this reaction is substantially greater than unity for irradiation at 270 and 365 nm, except when dissolved chlorine is present, and that the primary photoprocess is redox in nature. Accordingly, a chain mechanism involving homolytic bond cleavage of hexachloroplatinate(IV) to yield atomic chlorine and a labile platinum(III) species is proposed to account for the observed behavior. Support for the suggested reaction pathway includes evidence based on chemical scavenging experiments for the presence of chlorine atoms. In contrast to previous work on the photohydrolysis of hexabromoplatinate(IV), which occurs by a non-chain, non-redox process and which involves the lowest energy ligand-field triplet state, our results indicate that the charge-transfer singlet state is active in the photoaquation of hexachloroplatinate(IV).

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