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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

From National Research Council Canada

DOIResolve DOI: https://doi.org/10.1021/jo102420p
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Affiliation
  1. National Research Council of Canada. National Institute for Nanotechnology
FormatText, Article
Subjectacetonitrile 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
Abstract
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.
Publication date
In
  • Journal of Organic Chemistry 76, no. 6: 1789–1794.
LanguageEnglish
Peer reviewedYes
NPARC number21271145
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Record identifier986305f1-a63f-4a75-a073-6c8a636a8e77
Record created2014-03-24
Record modified2020-04-21
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