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Article << Previous     |     Next >>   Contents Vol 66(3)

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


 
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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.





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