Quantum Chemical Investigation of Mechanisms of Silane Oxidation

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• 作者：Mary M. Mader and Per-Ola Norrby
• 刊名：Journal of the American Chemical Society
• 出版年：2001
• 出版时间：March 7, 2001
• 年：2001
• 卷：123
• 期：9
• 页码：1970 - 1976
• 全文大小：100K
• 年卷期：v.123,no.9(March 7, 2001)
• ISSN：1520-5126

文摘

Several mechanisms for the peroxide oxidation of organosilanes to alcohols are compared by quantumchemical calculations, including solvation with the PCM method. Without doubt, the reaction proceeds viaanionic, pentacoordinate silicate species, but a profound difference is found between in vacuo and solvatedreaction profiles, as expected. In the solvents investigated (CH₂Cl₂ and MeOH), the most favorable mechanismis addition of peroxide anion to a fluorosilane (starting material or formed in situ), followed by a concertedmigration and dissociation of hydroxide anion. In the gas phase, and possibly in very nonpolar solvents, concertedaddition-migration of H₂O₂ to a pentacoordinate fluorosilicate is also plausible.