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Electrocatalysis and electron transfer mechanisms in the reduction of organic halides at Ag

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Abstract

The reductive cleavage of a series of organic halides, including both aromatic and aliphatic compounds, has been investigated in acetonitrile at glassy carbon (GC) and silver electrodes. Ag exhibits extraordinary electrocatalytic activities for the reduction of most of the investigated halides. During the reductive cleavage of a carbon–halogen bond, electron transfer (ET) and bond breaking may occur either in a single step or in two distinct steps. The compounds examined in this study are representative of both dissociative electron transfer (DET) mechanisms. In general a link between the DET mechanism and electrocatalysis at Ag is observed for the whole set of data. There is no catalysis at all when the ET involves a substituent that gives a stable radical anion. Furthermore, there is no catalysis for all aromatic chlorides. Instead, a remarkable electrocatalysis is observed for all compounds undergoing a concerted DET mechanism, regardless of the nature of the halogen atom.

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Acknowledgements

This work was financially supported by the Ministero dell’Istruzione, dell’Università e della Ricerca.

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Authors and Affiliations

  1. Department of Chemical Sciences, University of Padova, via Marzolo 1, 35131, Padova, Italy

    Abdirisak Ahmed Isse & Armando Gennaro

  2. Department of Physical Chemistry and Electrochemistry, University of Milano, via Golgi 19, 20133, Milan, Italy

    Giacomo Berzi, Luigi Falciola, Manuela Rossi & Patrizia R. Mussini

Authors
  1. Abdirisak Ahmed Isse
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  2. Giacomo Berzi
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  3. Luigi Falciola
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  4. Manuela Rossi
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  5. Patrizia R. Mussini
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  6. Armando Gennaro
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Correspondence to Armando Gennaro.

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Isse, A.A., Berzi, G., Falciola, L. et al. Electrocatalysis and electron transfer mechanisms in the reduction of organic halides at Ag. J Appl Electrochem 39, 2217–2225 (2009). https://doi.org/10.1007/s10800-008-9768-z

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  • DOI: https://doi.org/10.1007/s10800-008-9768-z

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