Spin chemistry of organometallic compounds 5

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• 作者：Marc B. Taraban ; Vladimir I. Rakhlin ; Olga S. Volkova ; Tatyana A. Podgorbunskaya ; Leonid V. Kuibida ; Rudolf G. Mirskov ; Tatyana V. Leshina ; Larisa V. Sherstyannikova ; Mikhail G. Voronkov
• 关键词：N-bromohexamethyl disilazane ; Silyl hydrides ; Silazanes ; Free radicals ; CIDNP
• 刊名：Journal of Organometallic Chemistry
• 出版年：2008
• 出版时间：15 December 2008
• 年：2008
• 卷：693
• 期：26
• 页码：3815-3820
• 全文大小：549 K

文摘

Reaction of N-bromohexamethyl disilazane (Me₃Si)₂NBr with substituted triorganyl silanes R¹R²R³SiH results in asymmetric disilazanes Me₃SiNHSiR¹R²R³ and bromination product, bromotrimethyl silane Me₃SiBr. The reaction has demonstrated an unusual dependence on specific solvation. In benzene, bromination occurs immediately after mixing of the reagents, while in cyclohexane, the reaction products are formed only under UV-irradiation. Application of photoinduced CIDNP method has shown that the mechanism of bromination of triorganyl silanes is comprised of a series of consecutive radical stages involving N-centered disilazanyl (Me₃Si)₂N and Si-centered silyl R¹R²R³Si radicals.