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Theoretical Study of the Hydrolysis of Iron–Sulfur–Nitrosyl Complex [Fe(NO)2(SCH2)2]+1статья
- Авторы: Luzhkov V.B., Krapivin V.B., Sanina N.A., Aldoshin S.M.
- Журнал: Russian Journal of Physical Chemistry A
- Том: 97
- Номер: 5
- Год издания: 2023
- Издательство: Pleiades Publishing, Ltd
- Местоположение издательства: Road Town, United Kingdom
- Первая страница: 813
- Последняя страница: 821
- DOI: 10.1134/s003602442305014x
- Аннотация: The mechanisms of hydrolysis of a model iron–sulfur–nitrosyl complex (ISNC)[Fe(NO)2(SCH 2 )2 ]+ 1 with thioformaldehyde ligands have been studied using the density functional theoryand polarizable continuum model of water. Quantum chemical calculations employed the TPSSH and M06functionals and def2-TZVP basis set and took into account interactions with water medium. Hydrolysis of 1was found to be an exothermic process with small activation energy whereas exchange of NO for H2 O is ther-modynamically unfavorable. The calculations have predicted lower activation barrier for the associativemechanism with concerted replacement of SCH2 by H2 O than for dissociative mechanism with homolyticbond cleavage of the Fe–S coordination bond in water. The mechanism of hydrolysis that involves participa-tion of OH – was found to be less probable at pH 7. The calculation results show that ISNC 1 is of{Fe 1+(NO•)2} 9 type and retains its tetrahedral structure that is typical for crystals of ISNC with thiocarbonylligands.
- Добавил в систему: Алдошин Сергей Михайлович