A computational study of the fluctional behaviour of group 14 substituted ortho-semiquinone radicals

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DOIResolve DOI: http://doi.org/10.1139/V10-082
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TypeArticle
Journal titleCanadian Journal of Chemistry
Volume89
Issue2
Pages235240; # of pages: 6
Subjectsemiquinone radicals; group migration; group-coupled electron transfer; kinetics; density functional theory; radicaux semiquinones; migration de groupe; transfert d'électron couplé à un groupe; cinétique; théorie de la fonctionnelle de la densité
AbstractThe dynamics of the 1,4-migration of some O-substituted 3,5-di-tert-butyl-ortho-semiquinone radicals have been calculated by density-functional theory (DFT). There is very good agreement in the rate constant and Arrhenius parameters between these calculations and experimental values for migration of H, D, and the Me₃Si group. For the Me₃Sn group, the calculations indicate an incredibly fast migration (k²⁹³K = 2.0 × 10¹² s⁻¹), a result that is consistent with experimental data (k²⁹³K > 10⁹ s⁻¹). Other O-substituents examined by DFT and compared with experimental data were H₃C and Me₂ClSn.
Publication date
LanguageEnglish
AffiliationNRC Steacie Institute for Molecular Sciences; National Institute for Nanotechnology; National Research Council Canada
Peer reviewedYes
NPARC number19739663
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Record identifierac7a6a51-94ae-4013-9426-cd463b4865c3
Record created2012-04-02
Record modified2016-05-09
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