Theoretical and Experimental Chemistry

, Volume 25, Issue 6, pp 633–637 | Cite as

Kinetics of symmetric electron exchange reaction in series of substituted nitrobenzenes: Influence of reactant structure

  • N. T. Ioffe
  • V. G. Mairanovskii
Article
  • 15 Downloads

Abstract

Kinetic data on symmetric electron exchange in substituted nitrobenzenes have been obtained by means of ESR. The logarithm of the electron exchange rate constant varies linearly with the square of the constant of hyperfine splitting on the nitrogen atom of the nitro group. On the basis of the results obtained, it is concluded tentatively that solvation of the nitro group plays a decisive role in the kinetics of symmetric electron exchange in this series of compounds.

Keywords

Nitrogen Exchange Rate Nitrogen Atom Exchange Reaction Nitrobenzene 

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Literature cited

  1. 1.
    L. Eberson, “Electron transfer reactions in organic chemistry,” Adv. Phys. Org. Chem., 18, 79–185 (1982).Google Scholar
  2. 2.
    G. Gramp and W. Jaenicke, “ESR-spectroscopic investigation of the homogeneous electron transfer reactions between substituted p-phenylenediamines and quinolinediimides, and the validity of the Marcus theory,” Ber. Bunsenges. Phys. Chem., 88, No. 2, 325–334 (1984).Google Scholar
  3. 3.
    C. Russel and W. Jaenicke, “Rate constants of activation, free enthalpies and activation entropies of the electrochemical reduction of 1,4-diazines in DMF,” Electrochim. Acta, 27, No. 2, 1445–1450 (1982).Google Scholar
  4. 4.
    M. E. Peover and J. S. Powell, “Dependence of electrode kinetics on molecular structure of nitro-compounds in dimethylformamide,” J. Electroanal. Chem., 20, No. 2, 427–433 (1969).Google Scholar
  5. 5.
    K. Suga and S. Aoyagui, “The applicability of the theory of R. A. Marcus to the electron transfer reactions between polycylic aromatic hydrocarbons and their anion radicals,” Bull. Chem. Soc. Jpn., 46, No. 3, 755–761 (1973).Google Scholar
  6. 6.
    Yu. I. Kharkats, “Calculation of solvent reorganization energy in reactions of inner-sphere charge transfer,” Élektrokhimiya, 10, No. 7, 1251–1260 (1974).Google Scholar
  7. 7.
    Yu. I. Kharkats, “Calculation of solvent reorganization energy in model of prolate ellipsoid of revolution,” Élektrokhimiya, 15, No. 8, 1251–1260 (1979).Google Scholar
  8. 8.
    N. T. Ioffe and V. G. Mairanovskii, “Cell for kinetic studies of electron exchange reactions by electrochemistry-ESR method (ESR-EL),” Élektrokhimiya, 22, No. 12, 1695–1697 (1986).Google Scholar
  9. 9.
    S. Chen Kuang and Noboru Hirota, Electron Paramagnetic Resonance: Methods for Investigation of Fast Reactions [Russian translation], Mir, Moscow (1977), pp. 626–688.Google Scholar
  10. 10.
    A. J. Gordon and R. A. Ford, The Chemist's Companion, Wiley, New York (1972).Google Scholar
  11. 11.
    N. M. Katkova and S. M. Shein, “Rate constants of electron transfer between p-nitroanisole, p-nitrophenyltrifluoromethanesulfonate, and p-nitrobenzaldehyde and their anion radicals,” Kinet. Katal., 13, No. 2, 402–403 (1972).Google Scholar
  12. 12.
    T. Layloff, T. Miller, and R. N. Agens, “Homogeneous electron exchange reactions of aromatic molecules,” Nature, 205, No. 4969, 382–383 (1965).Google Scholar
  13. 13.
    Yu. M. Kargin, S. V. Kuzovenko, L. Z. Manapova, and L. M. Vorontsova, “Free energy of activation for reaction of reduction of aromatic nitro compounds,” Élektrokhimiya, 22, No. 8, 1199–1201 (1986).Google Scholar

Copyright information

© Plenum Publishing Corporation 1990

Authors and Affiliations

  • N. T. Ioffe
    • 1
  • V. G. Mairanovskii
    • 1
  1. 1.Scientific-Industrial Association “Vitaminy”Moscow

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