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Mader MM, Norrby PO. Quantum chemical investigation of mechanisms of silane oxidation. J Am Chem Soc. 2001;123(9):1970-6doi: 10.1021/ja001400p.
Mader, M. M., & Norrby, P. O. (2001). Quantum chemical investigation of mechanisms of silane oxidation. Journal of the American Chemical Society, 123(9), 1970-6. https://doi.org/10.1021/ja001400p
Mader, M M, and Norrby, P O. "Quantum chemical investigation of mechanisms of silane oxidation." Journal of the American Chemical Society vol. 123,9 (2001): 1970-6. doi: https://doi.org/10.1021/ja001400p
Mader MM, Norrby PO. Quantum chemical investigation of mechanisms of silane oxidation. J Am Chem Soc. 2001 Mar 07;123(9):1970-6. doi: 10.1021/ja001400p. PMID: 11456818.
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J Am Chem Soc. 2001 Mar 07;123(9):1970-6. doi: 10.1021/ja001400p.

Quantum chemical investigation of mechanisms of silane oxidation.

Journal of the American Chemical Society

M M Mader, P O Norrby

Affiliations

  1. Department of Chemistry, Grinnell College, Grinnell, Iowa 50112, USA. [email protected]

PMID: 11456818 DOI: 10.1021/ja001400p

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 (CH(2)Cl(2) 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 H(2)O(2) to a pentacoordinate fluorosilicate is also plausible.

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