Uncommon aqueous media for nitrilimine cycloadditions. II. Computational study of the effect of water on reaction rate (Articolo in rivista)

Type
Label
  • Uncommon aqueous media for nitrilimine cycloadditions. II. Computational study of the effect of water on reaction rate (Articolo in rivista) (literal)
Anno
  • 2002-01-01T00:00:00+01:00 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#doi
  • 10.1039/b205071d (literal)
Alternative label
  • Ponti A., Molteni G. (2002)
    Uncommon aqueous media for nitrilimine cycloadditions. II. Computational study of the effect of water on reaction rate
    in New journal of chemistry (1987)
    (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#autori
  • Ponti A., Molteni G. (literal)
Pagina inizio
  • 1346 (literal)
Pagina fine
  • 1351 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#numeroVolume
  • 26 (literal)
Rivista
Note
  • ISI Web of Science (WOS) (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#affiliazioni
  • Istituto di Scienze e Tecnologie Molecolari, Consiglio Nazionale delle Ricerche, via Golgi 19, 20133, Milano, Italy. E-mail: ponti@istm.cnr.it; Fax: +39 02 5031 4300 Universita` degli Studi di Milano, Dipartimento di Chimica Organica e Industriale, via Golgi 19, 20133, Milano, Italy (literal)
Titolo
  • Uncommon aqueous media for nitrilimine cycloadditions. II. Computational study of the effect of water on reaction rate (literal)
Abstract
  • The effect of water on the 1,3-dipolar cycloaddition reaction of nitrilimines to alkenes has been studied by HF and DFT ab initio calculations. As solvation models we used the polarizable continuum model and a model comprising small clusters consisting of reactants hydrogen-bonded to water molecules. In addition, a combination of these two models was considered. Reactivity has been qualitatively estimated by the familiar frontier molecular orbital approach and quantitatively computed by a recent extension to the hard-soft acid-base principle involving molecular reactivity indices. The main conclusions drawn from the extensive computational results are that (i) the effect of water is in general rather small and (ii) therefore, water is not directly responsible for the large acceleration of the 1,3-dipolar cycloaddition reaction of nitrilimines to alkenes. Its role is surely minor with respect to that played by the ionic catalysts present in the reaction mixture, in agreement with the conclusions drawn in the experimental companion paper. (literal)
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