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Electron Transfer II pp 125–145Cite as

One-electron redox reactions between radicals and organic molecules. An addition/elimination (inner-sphere) path [1]

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Part of the book series: Topics in Current Chemistry ((TOPCURRCHEM,volume 177))

Abstract

In aqueous solution the electron transfer between (reducing) carbon-centered radicals or (oxidizing) hetero-atom-centered inorganic radicals and organic molecules often proceeds by covalent bond formation between the radical and the molecule followed by heterolysis of the so-formed bond between the carbon and the hetero-atom. It is the heterolysis step in which the actual electron transfer between the radical and the molecule takes place. This makes electron transfer a part of the area of (heterolytic) solvolysis reactions. The rate constant for the heterolysis is sensitive to and therefore indicative of the difference in effective electron density or affinity between the radical and the molecule. Factors such as substituents or protonation/deprotonation by which the electron density or distribution is changed strongly influence the rates of heterolysis of the adducts. The observed structure-activity relations for heterolysis of the radical-molecule adducts and thus the electron transfer between the adduct components can be rationalized in terms of the classical solvolysis concepts.

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5 References and Notes

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  1. Max-Planck-Institut für Strahlenchemie, Stiftstrasse 34–36, D-45470, Mülheim, Germany

    Steen Steenken

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J. Mattay

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© 1996 Springer-Verlag

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Steenken, S. (1996). One-electron redox reactions between radicals and organic molecules. An addition/elimination (inner-sphere) path [1]. In: Mattay, J. (eds) Electron Transfer II. Topics in Current Chemistry, vol 177. Springer, Berlin, Heidelberg. https://doi.org/10.1007/3-540-60110-4_4

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  • DOI: https://doi.org/10.1007/3-540-60110-4_4

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