Data di Pubblicazione:
2015
Citazione:
The solvent effect on the electrocatalytic cleavage of carbon-halogen bonds on Ag and Au / S. Arnaboldi, A. Gennaro, A.A. Isse, P.R. Mussini. - In: ELECTROCHIMICA ACTA. - ISSN 0013-4686. - 158(2015 Mar 10), pp. 427-436.
Abstract:
In recent years it has been shown in detail how the electrocatalytic cleavage of carbonhalogen
bonds is modulated by (a) the stepwise or concerted nature of the dissociative electrontransfer
mechanism, which is influenced by the nature of the electrode surface, the type of halogen
atom and the molecular structure of RX as a whole, and (b) the double-layer structure (as a function of
the nature and bulkiness of the supporting electrolyte ions). In order to both complete and support the
interpretative scheme thus developed, this work is focused on the solvent role. When one compares
aprotic with protic organic solvents after appropriate intersolvental normalization, interesting
peculiarities emerge, especially concerning protic media. Solvent proticity deeply affects both the
reaction mechanism (on both non-catalytic and catalytic electrodes) and the extent of the catalytic
effects. These items are discussed on the basis of a complete investigation carried out with a carefully
controlled experimental protocol on two chloride and bromide couples, one aromatic and one
aliphatic, representative of stepwise and concerted mechanisms, respectively, in four aprotic and four protic solvents, on both non-catalytic GC and catalytic Ag and Au electrodes. The results are discussed in the framework of a recently developed interpretative scheme of the carbon-halogen cleavage mechanism.
Tipologia IRIS:
01 - Articolo su periodico
Keywords:
Dissociative electron transfer, electrocatalysis, solvent effect, reductive cleavage, carbon-halogen bond
Elenco autori:
S. Arnaboldi, A. Gennaro, A.A. Isse, P.R. Mussini
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