Theoretical and Experimental Chemistry

, Volume 24, Issue 4, pp 487–490 | Cite as

Activation parameters of electron-transfer reactions with synchronous cleavage of a bond

  • Yu. A. Maletin
  • A. A. Dubinskaya
  • K. É. Gulyanitskii
Brief Communications


The temperature dependence of the rate constants of the disproportionation reactions of verdazyl radicals (R') in their complexes with zinc ions and of the inner-sphere oxidation of copper(I) by tetraethylthiuram disulfide (tds) in acetonitrile and mixtures of the latter with benzene has been measured. The activation parameters of the reactions studied have been determined according to the Arrhenius equation. In these reactions electron transfer is accompanied by the synchronous cleavage of a chemical bond [Zn-R in the complex Zn(R')22+ or S-S in tds], which is manifested by a decrease in the value of the preexponential factor. It has been established that the dependence of the rate constants on the polarity of the medium does not conform to the framework of Marcus' theory, but the activation energy and the preexponential factor decrease symbatically and approximately exponentially as the mole fraction of the polar molecules of acetonitrile in its mixtures with benzene is increased.


Zinc Benzene Activation Energy Acetonitrile Disulfide 
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Literature cited

  1. 1.
    Y. A. Maletin and N. G. Strizhakova, “Kinetics and mechanism of electron transfer via bridge metal-ion,” Int. J. Chem. Kinet. 18, No. 1, 13–29 (1986).Google Scholar
  2. 2.
    D. V. Matyushov and Yu. A. Maletin, “Inner-sphere electron transfer ccompanied by cleavage of a metal-ligand bond,” Dokl. Akad. Nauk UkrSSR, Ser. B, No. 2, 52–55 (1988).Google Scholar
  3. 3.
    C. P. Andrieux, J.-M. SavÉant, and K. B. Su, “Kinetics of dissociative electron transfer. Direct and mediated electrochemical reductive cleavage of the carbon-halogen bond,” J. Phys. Chem., 90, No. 16, 3815–3823 (1986).Google Scholar
  4. 4.
    Yu. A. Maletin, N. G. Strizhakova, T. V. Verkhovlyuk, and I. A. Sheka, “Kinetics and mechanism of the oxidation of copper(I) ions by thiuram sulfide,” Teor. Éksp. Khim., 24, No. 4, 450–455 (1988).Google Scholar
  5. 5.
    D. F. Calef and P. G. Wolynes, “Classical solvent dynamics and electron transfer. 1. Continuum theory,” J. Phys. Chem., 87, No. 18, 3387–3400 (1983).Google Scholar
  6. 6.
    I. L. Karle, J. A. Estlin, and K. Britts, “The crystal and molecular structure of tetra-ethylthiuram disulfide C10H20N2S4,” Acta Crystallogr., 22, No. 2, 273–280 (1967).Google Scholar
  7. 7.
    A. I. Karasevskii, D. V. Matyushov, and A. V. Gorodyskii, “Radiationless transitions in systems with mobile defects and the occurrence of oxidation-reduction reactions,” Dokl. Akad. Nauk SSSR, 297, No. 5, 1156–1158 (1987).Google Scholar

Copyright information

© Plenum Publishing Corporation 1989

Authors and Affiliations

  • Yu. A. Maletin
    • 1
  • A. A. Dubinskaya
    • 1
  • K. É. Gulyanitskii
    • 1
  1. 1.Institute of General and Inorganic ChemistryAcademy of Sciences of the Ukrainian SSRKiev

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