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Reactions of Organic Compounds at Electrodes

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Electrochemistry in Organic Synthesis

Abstract

Reactive intermediates (radicals, radical ions and ions) which result by an electron transfer may be expected in the region of redox potentials of corresponding electrophores (electroactive atoms or groups of atoms in organic substrates). The precise values of these potentials in actual compounds are always stated for a given electrode, a given supporting electrolyte, a given solvent and are measured versus a suitable reference electrode, most frequently a SCE. An informative, very approximate idea about the potential ranges in which the electrochemical redox transformations of different types of substrates occur is shown in Fig. 3.1. Electrochemical reactions of organic compounds whose redox potentials lie in close vicinity to potentials attainable by electrochemical methods are very difficult to perform in a direct way. In particular in oxidative processes performed at high positive potentials a number of side reactions may proceed (oxidation of the solvent or of the supporting electrolyte) which lower the selectivity of the product formation and hence also the material and current yield, or deactivate the working electrodes by forming polymeric films on the electrode surface.

Potential range of oxidation and reduction of some electrophors (vs SCE)

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Volke, J., Liška, F. (1994). Reactions of Organic Compounds at Electrodes. In: Electrochemistry in Organic Synthesis. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-78699-0_3

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