Rate coefficients for intramolecular homolytic substitution of oxyacyl radicals at selenium

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

Research output: Contribution to journalArticlepeer-review

12 Citations (Scopus)

Abstract

Ab initio and density functional calculations predict that intramolecular homolytic substitution reactions of oxyacyl radicals at the selenium atom in ω-alkylseleno-substituted radicals proceed via mechanisms that do not involve hypervalent intermediates. When the leaving radical is tert-butyl, energy barriers (ΔG-) for these reactions range from 27.1 (G3(MP2)-RAD) kJ mol-1 for the formation of the five-membered cyclic selenocarbonate (6) to 41.5 kJ mol-1 for the six-membered selenocarbonate (8). G3(MP2)-RAD calculations predict rate coefficients in the order of 105-108 s-1 and 102-10 5 s-1 for the formation of 6 and 8, respectively, at 298.15 K in the gas phase.

Original languageEnglish
Pages (from-to)51-58
Number of pages8
JournalInternational Journal of Chemical Kinetics
Volume44
Issue number1
DOIs
Publication statusPublished - Jan 2012
Externally publishedYes

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