A time-resolved kinetic study of the reactions of ring-substituted cumyloxyl radicals (4-X-CumO•: X = OMe, t-Bu, Me, Cl, CF3) with methylferrocenes (MenFc: n = 2, 8, 10) has been carried out in acetonitrile solution. Evidence for an electron transfer (ET) process has been obtained for all radicals and an increase in reactivity has been observed on decreasing the oxidation potential of the ferrocene donor and on going from electron-releasing to electron-withdrawing ring substituents. Computations predict the formation of strongly bound π-stacked 4-X-CumO•/DcMFc complexes, characterized by intracomplex π−π distances around 4 Å. These findings point toward a (nonbonded) inner-sphere ET mechanism for the reactions of the 4-X-CumO•/MenFc couples.

Bietti, M., Dilabio, G., Lanzalunga, O., Salamone, M. (2011). Time-Resolved Kinetic Study of the Electron Transfer Reactions Between Ring-Substituted Cumyloxyl Radicals and Alkyl Ferrocenes. Evidence for an Inner-Sphere Mechanism. JOURNAL OF ORGANIC CHEMISTRY, 76, 1789-1794 [10.1021/jo102420p].

Time-Resolved Kinetic Study of the Electron Transfer Reactions Between Ring-Substituted Cumyloxyl Radicals and Alkyl Ferrocenes. Evidence for an Inner-Sphere Mechanism

BIETTI, MASSIMO;SALAMONE, MICHELA
2011-02-24

Abstract

A time-resolved kinetic study of the reactions of ring-substituted cumyloxyl radicals (4-X-CumO•: X = OMe, t-Bu, Me, Cl, CF3) with methylferrocenes (MenFc: n = 2, 8, 10) has been carried out in acetonitrile solution. Evidence for an electron transfer (ET) process has been obtained for all radicals and an increase in reactivity has been observed on decreasing the oxidation potential of the ferrocene donor and on going from electron-releasing to electron-withdrawing ring substituents. Computations predict the formation of strongly bound π-stacked 4-X-CumO•/DcMFc complexes, characterized by intracomplex π−π distances around 4 Å. These findings point toward a (nonbonded) inner-sphere ET mechanism for the reactions of the 4-X-CumO•/MenFc couples.
24-feb-2011
Pubblicato
Rilevanza internazionale
Articolo
Sì, ma tipo non specificato
Settore CHIM/06 - CHIMICA ORGANICA
English
Con Impact Factor ISI
Bietti, M., Dilabio, G., Lanzalunga, O., Salamone, M. (2011). Time-Resolved Kinetic Study of the Electron Transfer Reactions Between Ring-Substituted Cumyloxyl Radicals and Alkyl Ferrocenes. Evidence for an Inner-Sphere Mechanism. JOURNAL OF ORGANIC CHEMISTRY, 76, 1789-1794 [10.1021/jo102420p].
Bietti, M; Dilabio, G; Lanzalunga, O; Salamone, M
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2108/13180
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