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

Michelle Coote 1 Christopher Easton 1 Samir Zard 2
1 ARC Centre of Excellence in Free Radical Chemistry and Biotechnology
2 DCSO - Laboratoire de synthèse organique
Abstract : High-level ab initio calculations demonstrate that alkoxythiocarbonyl radicals (ROC.=S) undergo ß-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. © 2006 American Chemical Society.
Document type :
Journal articles
Complete list of metadatas
https://hal-polytechnique.archives-ouvertes.fr/hal-00951308
Contributor : Denis Roura <>
Submitted on : Monday, March 3, 2014 - 3:04:18 PM
Last modification on : Thursday, February 7, 2019 - 5:10:36 PM

Links full text

istex

Identifiers

Collections

CNRS | X-DCSO | X | PARISTECH | INC-CNRS | X-DEP-CHIM

Citation

Michelle Coote, Christopher Easton, Samir Zard. Factors affecting the relative and absolute rates of ß-scission of alkoxythiocarbonyl radicals and alkoxycarbonyl radicals. Journal of Organic Chemistry, American Chemical Society, 2006, 71 (13), pp.4996-4999. ⟨10.1021/jo0607313⟩. ⟨hal-00951308⟩

Export

BibTeX TEI DC DCterms EndNote

Share

Metrics

Record views

131

Contact

CCSD