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Structure and reactivity of the radical cations of methyl tert-butyl ether in condensed phase: An ESR and quantum chemical studyстатья
Информация о цитировании статьи получена из
Web of Science,
Scopus
Статья опубликована в журнале из списка Web of Science и/или Scopus
Дата последнего поиска статьи во внешних источниках: 18 июля 2013 г.
- Авторы: Tyurin D.A., Belevskii V.N.
- Журнал: High Energy Chemistry
- Том: 35
- Номер: 6
- Год издания: 2001
- Издательство: Pleiades Publishing, Ltd
- Местоположение издательства: Road Town, United Kingdom
- Первая страница: 404
- Последняя страница: 416
- DOI: 10.1023/A:1012534725443
- Аннотация: The structure of the methyl tert-butyl ether (MTBE) radical cation and mechanism of its thermal and photochemical reactions in irradiated freons (CFCl3, CF2ClCFCl2, and CF3CCl3) were studied. Radical products of MTBE radiolysis in the liquid phase were investigated by the spin trapping technique. The quantum-chemical calculations of the structure of MTBE radical cations and products of their transformations were carried out by density functional theory (DFT) and ab initio MP2 methods. The primary MTBE radical cations are stabilized in dilute solutions in CFCl3 and CF3CCl3. The ion-molecule reaction (proton transfer from the radical cation) was found to occur in concentrated solutions in CFCl3 immediately during irradiation. The action of light (lambda = 436 to 546 nm) at 77 K on the MTBE radical cation in CFCl3 and CF3CCl3 matrices results in intramolecular migration of the methyl group to yield the distonic radical cation (CH3)(2)(CO+)-C-.(CH3)(2). The primary MTBE radical cations undergo an irreversible transformation with methane elimination resulting in formation of the 2-methoxypropene radical cation (CH2)-C-. =C+(CH3)OCH3 in CFCl3 and CF3CCl3 matrices in the temperature range 110-130 K. In the case of CF2ClCFCl2 matrix, such a reaction occurs during irradiation at 77 K. Using the spin trapping technique, it was shown that the liquid-phase radiolysis of the neat ether resulted in the formation of fragmentation products ((CH3)-C-., CH3O., and t-BuO. radicals) from the primary radical cations, as well as the products of their rearrangements and ion-molecule reactions.
- Добавил в систему: Тюрин Даниил Александрович