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One-electron reduction of aromatic halides and the solvent effects on the unimolecular dissociation of the radical anion

Authors
Journal
International Journal of Radiation Applications and Instrumentation Part C Radiation Physics and Chemistry
1359-0197
Publisher
Elsevier
Publication Date
Volume
29
Issue
3
Identifiers
DOI: 10.1016/1359-0197(87)90113-5

Abstract

Abstract One-electron reduction of aromatic halides has been investigated by a pulse radiolysis technique in dipolar aprotic solvents. The transient absorption spectra observed immediately after the pulse irradiation to halobiphenyls, halonaphthalenes, or haloanthracenes have an absorption band which is assigned to the corresponding radical anion of the aromatic halides. The decay behavior of these bands followed first-order kinetics and the rates changed over three orders of magnitude depending upon the nature of the halide (Br, Cl), the position of a halogen atom on the aromatic ring, and the polarity of the solvent. These effects are rationalized in terms of spin density, charge distribution, and the C–X bond dissociation energy of the radical anion.

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