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The PtBr62− complex in methanol: thermal solvation and photochemistry in the presence of free bromide ions Научная публикация

Журнал Russian Chemical Bulletin
ISSN: 1066-5285
Вых. Данные Год: 2025, Том: 74, Номер: 10, Страницы: 2996-3006 Страниц : 11 DOI: 10.1007/s11172-025-4781-5
Авторы Malakhova Yu.A. 1,2 , Tamozhnikova V.S. 1 , Grivin V.P. 1 , Yakush E.A. 1 , Tsentalovich Yu.P. 3 , Glebov E.M. 1
Организации
1 V. V. Voevodsky Institute of Chemical Kinetics and Combustion, Siberian Branch of the Russian Academy of Sciences, 3 ul. Institutskaya, 630090, Novosibirsk, Russian Federation
2 Dresden University of Technology, 01069, Dresden, Germany
3 International Tomography Center, Siberian Branch of the Russian Academy of Sciences, 3a ul. Institutskaya, 630090, Novosibirsk, Russian Federation

Реферат: 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.
Библиографическая ссылка: 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
Даты:
Поступила в редакцию: 27 янв. 2025 г.
Принята к публикации: 23 июл. 2025 г.
Опубликована в печати: 19 нояб. 2025 г.
Идентификаторы БД:
Web of science: WOS:001618041200001
OpenAlex: W7105996810
Цитирование в БД: Пока нет цитирований
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