title: Factors affecting the relative and absolute rates of beta-scission of alkoxythiocarbonyl radicals and alkoxycarbonyl radicals.
abstract: High-level ab initio calculations demonstrate that alkoxy-thiocarbonyl radicals (ROC*=S) undergo beta-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.
authors.affiliation: ARC Centre of Excellence in Free Radical Chemistry and Biotechnology, Research School of Chemistry, Australian National University, Canberra, ACT 0200, Australia. mcoote@rsc.anu.edu.au
authors.forename: Michelle L
authors.initials: ML
authors.lastname: Coote
authors.forename: Christopher J
authors.initials: CJ
authors.lastname: Easton
authors.forename: Samir Z
authors.initials: SZ
authors.lastname: Zard