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dc.contributor.authorMeneses, Ana Belénen_US
dc.contributor.authorAntonello, Sabrinaen_US
dc.contributor.authorArévalo, María Carmenen_US
dc.contributor.authorGonzález Martín, Concepción C.en_US
dc.contributor.authorSharma, Jadaben_US
dc.contributor.authorWallette, Andrea N.en_US
dc.contributor.authorWorkentin, Mark S.en_US
dc.contributor.authorMaran, Flavioen_US
dc.identifier.citationChemistry - A European Journal 13(28): 7983-7995 (2007)en_US
dc.description13 pages, 7 figures, 5 tables.-- PMID: 17616962 [PubMed].-
dc.description.abstractThe electron-acceptor properties of series of related sulfides and disulfides were investigated in N,N-dimethylformamide with homogeneous (redox catalysis) and/or heterogeneous (cyclic voltammetry and convolution analysis) electrochemical techniques. The electron-transfer rate constants were determined as a function of the reaction free energy and the corresponding intrinsic barriers were determined. The dependence of relevant thermodynamic and kinetic parameters on substituents was assessed. The kinetic data were also analyzed in relation to corresponding data pertaining to reduction of diaryl disulfides. All investigated reductions take place by stepwise dissociative electron transfer (DET) which causes cleavage of the C(alkyl)-S or S-S bond. A generalized picture of how the intrinsic electron-transfer barrier depends on molecular features, ring substituents, and the presence of spacers between the frangible bond and aromatic groups was established. The reduction mechanism was found to undergo a progressive (and now predictable) transition between common stepwise DET and DET proceeding through formation of loose radical anions. The intrinsic barriers were compared with available results for ET to several classes of dissociative- and nondissociative-type acceptors, and this led to verification that the heterogeneous and the homogeneous data correlate as predicted by the Hush theory.-
dc.description.sponsorshipThis work was financially supported by the Ministero dell’Istruzione, dell’Università e della Ricerca (MIUR, Italy), the Integrated Action Italy-Spain between the University of Padova and the Universidad de La Laguna, and the Natural Science and Engineering Research Council (NSERC) of Canada. A.B.M. is thankful to the Universidad de La Laguna y Caja Canarias for a PhD grant.-
dc.format.extent2373 bytes-
dc.format.extent220587 bytes-
dc.publisherJohn Wiley & Sons-
dc.subjectElectron transfer-
dc.subjectSubstituent effects-
dc.titleElectron transfer to sulfides and disulfides: intrinsic barriers and relationship between heterogeneous and homogeneous electron-transfer kineticsen_US
dc.contributor.funderNatural Sciences and Engineering Research Council of Canada-
dc.contributor.funderUniversidad de La Laguna-
dc.contributor.funderCaja Canarias-
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