The reductive cleavage of a series of organic halides, including both aromatic and aliphatic compounds, has been investigated in acetonitrile at glassy carbon 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.

Electrocatalysis and electron transfer mechanisms in the reduction of organic halides at Ag / A. A. Isse, G. Berzi, L. Falciola, M. Rossi, P. R. Mussini, A. Gennaro. - In: JOURNAL OF APPLIED ELECTROCHEMISTRY. - ISSN 0021-891X. - 39:11(2009), pp. 2217-2225.

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

L. Falciola;M. Rossi;P. R. Mussini;
2009

Abstract

The reductive cleavage of a series of organic halides, including both aromatic and aliphatic compounds, has been investigated in acetonitrile at glassy carbon 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.
Dissociative electron transfer; Electrocatalysis; Organic halides; Silver electrode
Settore CHIM/01 - Chimica Analitica
JOURNAL OF APPLIED ELECTROCHEMISTRY
Article (author)
File in questo prodotto:
File Dimensione Formato  
Mussini Gennaro JAE.pdf

accesso aperto

321.37 kB Adobe PDF Visualizza/Apri
Pubblicazioni consigliate

Caricamento pubblicazioni consigliate

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/2434/62642
Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 82
  • ???jsp.display-item.citation.isi??? 75
social impact