Australian Journal of Chemistry Australian Journal of Chemistry Society
An international journal for chemical science
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Rate Coefficients for Intramolecular Homolytic Substitution of Oxyacyl Radicals at Sulfur

Heather M. Aitken A B , Sonia M. Horvat A B , Michelle L. Coote A C , Ching Yeh Lin A C and Carl H. Schiesser A B D

A ARC Centre of Excellence for Free Radical Chemistry and Biotechnology, Australia.

B School of Chemistry and Bio21 Molecular Science and Biotechnology Institute, The University of Melbourne, Melbourne, Vic. 3010, Australia.

C Research School of Chemistry, Australian National University, Canberra, ACT 0200, Australia.

D Corresponding author. Email: carlhs@unimelb.edu.au

Australian Journal of Chemistry 66(3) 323-329 http://dx.doi.org/10.1071/CH12477
Submitted: 19 October 2012  Accepted: 29 November 2012   Published: 18 January 2013

Abstract

It is predicted on the basis of ab initio and density functional calculations that intramolecular homolytic substitution of oxyacyl radicals at the sulfur atom in ω-alkylthio-substituted radicals do not involve hypervalent intermediates. With tert-butyl as the leaving radical, free energy barriers ΔG (G3(MP2)-RAD) for these reactions range from 45.8 kJ mol–1 for the formation of the five-membered cyclic thiocarbonate (8) to 56.7 kJ mol–1 for the formation of the six-membered thiocarbonate (9). Rate coefficients in the order of 104–106 s–1 and 101–104 s–1 for the formation of 8 and 9, respectively, at 353.15 K in the gas phase are predicted at the G3(MP2)-RAD level of theory.

Graphical Abstract Image


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