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Theoretical study on the unimolecular decomposition of thiophenol

Al-Muhtaseb, A.H., Altarawneh, M.ORCID: 0000-0002-2832-3886, Almatarneh, M.H., Poirier, R.A. and Assaf, N.W. (2011) Theoretical study on the unimolecular decomposition of thiophenol. Journal of Computational Chemistry, 32 (12). pp. 2708-2715.

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The potential energy surface for the unimolecular decomposition of thiophenol (C 6H 5SH) is mapped out at two theoretical levels; BB1K/GTlarge and QCISD(T)/6-311+G(2d,p)//MP2/6-31G(d,p). Calculated reaction rate constants at the high pressure limit indicate that the major initial channel is the formation of C 6H 6S at all temperatures. Above 1000 K, the contribution from direct fission of the Si-H bond becomes important. Other decomposition channels, including expulsion of H 2 and H 2S are of negligible importance. The formation of C 6H 6S is predicted to be strong-pressure dependent above 900 K. Further decomposition of C 6H 6S produces CS and C 5H 6. Overall, despite the significant difference in bond dissociation, i.e., 8-9 kcal/mol between the Si-H bond in thiophenol and the Oi-H bond in phenol, H migration at the ortho position in the two molecules represents the most accessible initial channel.

Item Type: Journal Article
Publisher: Wiley-Blackwell
Copyright: © 2011 Wiley Periodicals, Inc.
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