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Time-resolved kinetic study of the electron-transfer reactions between ring-substituted cumyloxyl radicals and alkylferrocenes. Evidence for an inner-sphere mechanism

Par Conseil national de recherches du Canada

DOITrouver le DOI : https://doi.org/10.1021/jo102420p
AuteurRechercher : ; Rechercher : 1; Rechercher : ; Rechercher :
Affiliation
  1. Conseil national de recherches du Canada. Institut national de nanotechnologie
FormatTexte, Article
Sujetacetonitrile solutions; electron transfer; electron-transfer reactions; electronwithdrawing; ferrocenes; innersphere mechanism; oxidation potentials; ring substituents; time-resolved kinetic study; acetonitrile; free radical reactions; iron compounds; kinetic theory; spheres; electrons; acetonitrile; cumyloxyl radical; ferrocene derivative; radical; unclassified drug; chemical bond; chemical reaction; complex formation; electrons; electron transport; kinetics; oxidation reduction potential
Résumé
A time-resolved kinetic study of the reactions of ring-substituted cumyloxyl radicals (4-X-CumO .: X = OMe, t-Bu, Me, Cl, CF 3) with methylferrocenes (Me NFc: n = 2, 8, 10) has been carried out in acetonitrile solution. Evidence for an electron transfer (ET) process has been obtained for all radicals and an increase in reactivity has been observed on decreasing the oxidation potential of the ferrocene donor and on going from electron-releasing to electron-withdrawing ring substituents. Computations predict the formation of strongly bound ?-stacked 4-X-CumO ./DcMFc complexes, characterized by intracomplex π-π distances around 4 Å. These findings point toward a (nonbonded) inner-sphere ET mechanism for the reactions of the 4-X-CumO ./Me nFc couples. © 2011 American Chemical Society.
Date de publication
Dans
  • Journal of Organic Chemistry 76, nº 6 : 1789–1794.
Langueanglais
Publications évaluées par des pairsOui
Numéro NPARC21271145
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Identificateur de l’enregistrement986305f1-a63f-4a75-a073-6c8a636a8e77
Enregistrement créé2014-03-24
Enregistrement modifié2020-04-21
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