Mechanism of thermal decomposition of allyltrichlorosilane with formation of three labile intermediates: dichlorosilylene, allyl radical, and atomic chlorine
- Авторы: Boganov S.1, Promyslov V.1, Krylova I.1, Zaitseva G.1,2, Egorov M.1
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Учреждения:
- N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences
- Department of Chemistry, M. V. Lomonosov Moscow State University
- Выпуск: Том 65, № 5 (2016)
- Страницы: 1216-1224
- Раздел: Full Articles
- URL: https://journals.rcsi.science/1066-5285/article/view/238059
- DOI: https://doi.org/10.1007/s11172-016-1438-4
- ID: 238059
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Аннотация
It is experimentally found that allyltrichlorosilane dissociates under vacuum pyrolysis (~10–2 Torr) at temperatures above 1100 K to form three labile intermediates: allyl radical, dichlorosilylene, and monoatomic chlorine. On the basis of experimental and theoretical data obtained, it is shown that the decomposition reaction proceeds in two steps. The first step is a typical reaction of homolytic decomposition to two radicals (C3H5 and SiCl3) at the weakest Si—C bond. Due to weakness of the Si—Cl bond in the SiCl3 radical, the energy of which is even somewhat lower than the dissociation energy of the Si—C bond in starting AllSiCl3, this radical undergoes further dissociation to SiCl2 and Cl, thus resulting in three intermediates of different classes of highly reactive species formed from AllSiCl3.
Об авторах
S. Boganov
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences
Автор, ответственный за переписку.
Email: bog@ioc.ac.ru
Россия, 47 Leninsky prosp., Moscow, 119991
V. Promyslov
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences
Email: bog@ioc.ac.ru
Россия, 47 Leninsky prosp., Moscow, 119991
I. Krylova
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences
Email: bog@ioc.ac.ru
Россия, 47 Leninsky prosp., Moscow, 119991
G. Zaitseva
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences; Department of Chemistry, M. V. Lomonosov Moscow State University
Email: bog@ioc.ac.ru
Россия, 47 Leninsky prosp., Moscow, 119991; 1/3 Leninskie Gory, Moscow, 119991
M. Egorov
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences
Email: bog@ioc.ac.ru
Россия, 47 Leninsky prosp., Moscow, 119991