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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According to the materials of the International Conference “Current Problems of Chemical Physics” (October 9–12, 2012, Yerevan (Republic of Armenia)).
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1540–1548, July, 2013.
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Glebov, E.M., Kolomeets, A.V., Pozdnyakov, I.P. et al. Chain processes in the photochemistry of PtIV halide complexes in aqueous solutions. Russ Chem Bull 62, 1540–1548 (2013). https://doi.org/10.1007/s11172-013-0221-z
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DOI: https://doi.org/10.1007/s11172-013-0221-z