IRIS Institutional Research Information System - AIR Archivio Istituzionale della Ricerca

IRIS è il sistema di gestione integrata dei dati della ricerca (persone, progetti, pubblicazioni, attività) adottato dall'Università degli Studi di Milano.

AIR nasce in UNIMI nel 2006 con lo scopo di raccogliere, documentare e conservare le informazioni sulla produzione scientifica dell'Università degli Studi di Milano e costituisce di fatto l'Anagrafe della ricerca dell'Ateneo.

The electrochem. redn. of arom. bromides including substituted bromobenzenes and polycyclic bromoarenes were studied in MeCN at Ag and glassy C (GC) electrodes. Whereas GC behaves as a noncatalytic electrode, Ag exhibits remarkable electrocatalytic activities for the redn. of all compds. The electrocatalytic effects are strongly influenced by the mol. structure of the arom. bromide, decreasing with increasing electron-withdrawing ability of the substituents as well as with extension of the polycyclic arom. system. Dissociative electron transfer (ET) to an org. halide RX may occur either in a single step (concerted mechanism) or in two distinct steps with the formation of an intermediate radical anion (stepwise mechanism). The mechanism of the redn. process was analyzed at both catalytic and noncatalytic electrodes. Electroredn. of all compds. at GC occurs according to a stepwise mechanism, whereas at Ag both mechanisms were obsd. depending on the structure of the mol. This study reports unprecedented examples of a passage from one dissociative ET mechanism to the other upon a change of the nature of the electrode material. The process at Ag involves adsorption of reagents, intermediates and products and is catalytic regardless of the mechanism of the dissociative ET. Anal. of the data herein reported together with literature data on the electroredn. of different types of org. halides sheds some light on the relation between catalysis and dissociative ET mechanism.

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