Factors affecting the relative and absolute rates of β-scission of alkoxythiocarbonyl radicals and alkoxycarbonyl radicals

Michelle L. Coote, Christopher J. Easton, Samir Z. Zard

Research output: Contribution to journalArticlepeer-review

19 Citations (Scopus)

Abstract

High-level ab initio calculations demonstrate that alkoxythiocarbonyl radicals (ROC.=S) undergo β-scission significantly faster than alkoxycarbonyl radicals (ROC.=O) despite having similar exothermicities. The relatively low reactivity of the ROC.=O radicals is reduced further by electron-donating R groups and arises from the large polarization of the C.-O bonds of the reactant radicals. The results suggest that the generation of alkyl radicals from ROC.=S should be particularly efficient when the R group bears radical-stabilizing and/or electron-accepting groups, such as CN.

Original languageEnglish
Pages (from-to)4996-4999
Number of pages4
JournalJournal of Organic Chemistry
Volume71
Issue number13
DOIs
Publication statusPublished - 1 Jun 2006
Externally publishedYes

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