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A DFT study of permanganate oxidation of toluene and its ortho -nitroderivatives

Adamczyk, Paweł ; Wijker, Reto ; Hofstetter, Thomas ; Paneth, Piotr

In: Journal of Molecular Modeling, 2014, vol. 20, no. 2, p. 1-13

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    Titre
    • A DFT study of permanganate oxidation of toluene and its ortho -nitroderivatives
    Auteur
    • Adamczyk, Paweł. Institute of Applied Radiation Chemistry, Faculty of Chemistry, Lodz University of Technology, Zeromskiego 116, 90-924, Lodz, Poland
    • Wijker, Reto. Eawag, Swiss Federal Institute of Aquatic Science and Technology, 8600, Dübendorf, Switzerland
    • Hofstetter, Thomas. Eawag, Swiss Federal Institute of Aquatic Science and Technology, 8600, Dübendorf, Switzerland
    • Paneth, Piotr. Institute of Applied Radiation Chemistry, Faculty of Chemistry, Lodz University of Technology, Zeromskiego 116, 90-924, Lodz, Poland
    Type de document
    • Postprint
    Langue
    • Inglese
    Publié dans
    • Journal of Molecular Modeling, 2014, vol. 20, no. 2, p. 1-13. Springer Berlin Heidelberg
    Autre version électronique
    Identifiant OAI-PMH
    • oai:doc.rero.ch:326356
    Summary
    Calculations of alternative oxidationpathways of toluene and its ortho-substituted nitro derivatives by permanganate anion have been performed. The competition between methyl group and ring oxidation has been addressed. Acceptable results have been obtained using IEFPCM/B3LYP/6-31+G(d,p) calculations with zero-point (ZPC) and thermal corrections, as validated by comparison with the experimental data. It has been shown that ring oxidation reactions proceed via relatively early transition states that become quite unsymmetrical for reactions involving ortho-nitrosubstituted derivatives. Transition states for the hydrogen atom abstraction reactions, on the other hand, are late. All favored reactions are characterized by the Gibbs free energy of activation, ΔG≠, of about 25kcal mol−1. Methyl group oxidations are exothermic by about 20kcal mol−1 while ring oxidations are around thermoneutrality. Figure Oxidation of toluene and its ortho-nitroderivatives