Abstract
The mechanisms of the photoaquation of PtCl6 2− and PtBr6 2− complexes were compared by the experimental results on stationary photolysis, nanosecond laser flash photolysis, and ultrafast pump-probe spectroscopy. The formation of the photoaquation product of the bromide complex, viz., PtBr5(H2O)−, was shown to proceed via the mechanism of heterolytic cleavage of the Pt-Br bond, and the platinum cation remained tetravalent in the course of the whole process. For the chloride complex, the Pt-Cl bond cleavage was found to be homolytic, and precursors of the photoaquation product, viz., PtCl5(H2O)− complex, are intermediates of trivalent platinum sequentially transforming into each other. The reactions of these intermediates determine the chain character of the photoaquation process.
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