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Electron Affinities of Quinones : Correlation of One-electron Redox Potentials with Quantum-mechanical Calculation

Naturevolume 193pages475476 (1962) | Download Citation



IN 1949, Maccoll1 showed that a linear relationship existed between the energy of the lowest unoccupied molecular orbitals of aromatic hydrocarbons (their electron affinities) and their polarographic half-wave potentials (E½). This relationship was further discussed and extended by Pullman et al.2 and Hoijtink3, although it was not always appreciated at that time that strictly only those E½ values obtained under conditions such that the reversible addition of one electron only (R + eR) is involved should be considered4; the potential is then virtually the standard potential for a one-electron addition. It has been suggested4 that such measurements for other aromatic molecules might provide equally valid parameters for certain properties, such as electron affinity, for which few independent estimates exist, and recently some E½ values of well-known electron acceptors were given with an indication of their possible application to charge-transfer studies5.

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  1. 1

    Maccoll, A., Nature, 163, 178 (1949).

  2. 2

    Pullman, A., Pullman, B., and Berthier, G., Bull. Soc. Chim. France, 591 (1950).

  3. 3

    Hoijtink, G. J., Rec. Trav. Chim., 74, 1525 (1955).

  4. 4

    Given, P. H., and Peover, M. E., Advances in Polarography, edit. by Longmuir, I. S., 948 (Pergamon Press, London, 1960).

  5. 5

    Peover, M. E., Nature, 191, 702 (1961).

  6. 6

    Nagakura, S., and Kuboyama, A., J. Amer. Chem. Soc., 76, 1003 (1954). Kuboyama, A., Bull. Chem. Soc. Japan, 31, 752 (1958); 32, 1226 (1959); 33, 917 (1960).

  7. 7

    Peover, M. E., paper submitted to J. Chem. Soc. (1962).

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  1. National Chemical Laboratory, Department of Scientific and Industrial Research, Teddington, Middx

    • M. E. PEOVER


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