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Article

Quantum Chemical Investigation of Mechanisms of Silane Oxidation

Supporting Info

Mary M. Mader*^† and Per-Ola Norrby*^‡

Contribution from the Department of Chemistry, Grinnell College, Grinnell, Iowa 50112, and Department of Medicinal Chemistry, The Royal Danish School of Pharmacy, Universitetsparken 2, DK-2100 Copenhagen, Denmark

J. Am. Chem. Soc., 2001, 123 (9), pp 1970–1976

DOI: 10.1021/ja001400p

Publication Date (Web): February 10, 2001

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

†

Grinnell College.; Current Address: Eli Lilly and Company, Lilly Corporate Center, Drop Code 1523, Indianapolis, IN 46285. E-mail: mader_mary@lilly.com.

‡

Royal Danish School of Pharmacy. Current address: Technical University of Denmark, Department of Organic Chemistry, Building 201, Kemitorvet, DK-2800 Lyngby, Denmark. E-mail: okpon@pop.dtu.dk.

Abstract

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

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