Rate Coefficients for Intramolecular Homolytic Substitution of Oxyacyl Radicals at Sulfur

Heather M. Aitken, Sonia M. Horvat, Michelle L. Coote, Ching Yeh Lin, Carl H. Schiesser

Research output: Contribution to journalArticlepeer-review

4 Citations (Scopus)

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 45.8kJmol-1 for the formation of the five-membered cyclic thiocarbonate (8) to 56.7kJmol-1 for the formation of the six-membered thiocarbonate (9). Rate coefficients in the order of 10 4-106s-1 and 101-10 4s-1 for the formation of 8 and 9, respectively, at 353.15K in the gas phase are predicted at the G3(MP2)-RAD level of theory.

Original languageEnglish
Pages (from-to)323-329
Number of pages7
JournalAustralian Journal of Chemistry
Volume66
Issue number3
DOIs
Publication statusPublished - 18 Jan 2013
Externally publishedYes

Bibliographical note

Funding Information:
We gratefully acknowledge support from the Australian Research Council (ARC) under their Centres of Excellence Scheme, generous allocations of computing time on the National Facility of the Australian National Computational Infrastructure, and the award (to MLC) of an ARC Future Fellowship.

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