Abstract: The mechanism of thermal solvation of the PtBr62− complex in methanol and the photochemistry of PtBr62− in methanol in the presence of free bromide ions were studied. It was established that thermal solvation of PtBr62− in methanol is a two-stage process with an autocatalytic second stage, which gives rise to S-shaped kinetic curves displaying the changes in the UV absorption spectra of PtBr62− solutions. A qualitative mechanism of the reaction is proposed. Steady-state photolysis and laser flash photolysis studies revealed that photoexcitation of PtBr62− in methanol in the presence of free Br− ions is accompanied by competing reactions, namely, photosolvation and two-electron photoreduction. The photoreduction is due to electron transfer from both solvent molecules and free bromide ions to the photoexcited complex to produce dihalide radical anions Br2•−. The reaction with the starting complex affording a pentavalent platinum intermediate contributes largely to the Br2•− decay. The values of the rate constant for this reaction in methanol and in water are discussed.

Cite: Malakhova Y.A. , Tamozhnikova V.S. , Grivin V.P. , Yakush E.A. , Tsentalovich Y.P. , Glebov E.M.
The PtBr62− complex in methanol: thermal solvation and photochemistry in the presence of free bromide ions
Russian Chemical Bulletin. 2025. V.74. N10. P.2996-3006. DOI: 10.1007/s11172-025-4781-5 WOS OpenAlex

Dates:

Submitted:	Jan 27, 2025
Accepted:	Jul 23, 2025
Published print:	Nov 19, 2025

Identifiers:

Web of science:	WOS:001618041200001
OpenAlex:	W7105996810

Citing: Пока нет цитирований

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