One-electron reduction of methanesulfonyl chloride. The fate of (MeSO2Cl)•– and MeSO2• intermediates in oxygenated solutions and their role in the cis-trans isomerization of monounsaturated fatty acids. (Articolo in rivista)

Type
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  • One-electron reduction of methanesulfonyl chloride. The fate of (MeSO2Cl)•– and MeSO2• intermediates in oxygenated solutions and their role in the cis-trans isomerization of monounsaturated fatty acids. (Articolo in rivista) (literal)
Anno
  • 2007-01-01T00:00:00+01:00 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#doi
  • 10.1021/ja070626q (literal)
Alternative label
  • Tamba, M.; Dajka, K.; Ferreri, C.; Asmus, K.-D.; Chatgilialoglu, C. (2007)
    One-electron reduction of methanesulfonyl chloride. The fate of (MeSO2Cl)•– and MeSO2• intermediates in oxygenated solutions and their role in the cis-trans isomerization of monounsaturated fatty acids.
    in Journal of the American Chemical Society (Print)
    (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#autori
  • Tamba, M.; Dajka, K.; Ferreri, C.; Asmus, K.-D.; Chatgilialoglu, C. (literal)
Pagina inizio
  • 8716 (literal)
Pagina fine
  • 8723 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#numeroVolume
  • 129 (literal)
Rivista
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#pagineTotali
  • 8 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#numeroFascicolo
  • 28 (literal)
Note
  • ISI Web of Science (WOS) (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#affiliazioni
  • K D Asmus Faculty of Chemistry, Adam Mickiewicz UniVersity, Grunwaldzka 6, 60-780 Poznan, Poland (literal)
Titolo
  • One-electron reduction of methanesulfonyl chloride. The fate of (MeSO2Cl)•– and MeSO2• intermediates in oxygenated solutions and their role in the cis-trans isomerization of monounsaturated fatty acids. (literal)
Abstract
  • The one-electron reduction of methanesulfonyl chloride (MeSO2Cl) leads, in the first instance, to an electron adduct MeSO2Cl¥- which lives long enough for direct detection and decays into sulfonyl radicals MeSO2 ¥ and Cl-, with k ) 1.5 ? 106 s-1. Both, MeSO2Cl¥- and MeSO2 ¥ showed a similar absorption in the UV with ìmax of 320 nm. In the presence of oxygen, MeSO2Cl¥- transfers an electron to O2 and establishes an equilibrium with superoxide. The rate constant for the forward reaction was measured to 4.1 ? 109 M-1 s-1, while for the back reaction only an interval of 1.7 ? 105 to 1.7 ? 106 M-1 s-1 could be estimated, with a somewhat higher degree of confidence for the lower value. This corresponds to an equilibrium constant in the range of 2.4 ? 103 to 2.4 ? 104. With reference to E° (O2/O2 ¥-) ) -155 mV, the redox potential of the sulfonyl chloride couple, E°(MeSO2Cl/MeSO2Cl¥-), thus results between being equal to -355 and -414 mV (vs NHE). MeSO2Cl¥- reduces (besides O2) 4-nitroacetophenone. The underlying electron transfer took place with k ) 1.5 ? 109 M-1 s-1, corroborating an E° for the sulfonyl chloride couple significantly exceeding the above listed lower value. The MeSO2 ¥ radical added to oxygen with a rate constant of 1.1 ? 109 M-1 s-1. Re-dissociation of O2 from MeSO2OO¥ occurred only very slowly, if at all, that is, with k , 105 s-1. MeSO2 ¥ radicals can act as the catalyst for the cis-trans isomerization of several Z- and E-mono-unsaturated fatty acid methyl esters in homogeneous solution. The effectiveness of the isomerization processes has been addressed, and in the presence of oxygen the isomerization is completely suppressed. Introduction Sulfur- (literal)
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