Mechanism of thermal decomposition of allyltrichlorosilane with formation of three labile intermediates: dichlorosilylene, allyl radical, and atomic chlorine

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• 作者：S. E. Boganov ; V. M. Promyslov ; I. V. Krylova ; G. S. Zaitseva…
• 关键词：Key wordsallyltrichlorosilane ; allyl radical ; dichlorosilylene ; trichlorosilyl radical ; matrix IR spectroscopy ; quantum chemical calculations ; G4(MP2) level
• 刊名：Russian Chemical Bulletin
• 出版年：2016
• 出版时间：May 2016
• 年：2016
• 卷：65
• 期：5
• 页码：1216-1224
• 全文大小：
• 刊物类别：Chemistry and Materials Science
• 刊物主题：Chemistry/Food Science, general; Organic Chemistry; Inorganic Chemistry;
• 出版者：Springer US
• ISSN：1573-9171
• 卷排序：65

文摘

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.