Intermolecular Electron Transfer Reactivity Determined from Cross-Rate Studies

Electron-transfer cross-reactions between neutral molecules and their radical cations spanning a wide range of structural type and intrinsic reactivity have been analyzed using classical Marcus theory. The principal factor found to govern intrinsic reactivity is the inner-shell bond reorganization e...

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Bibliographic Details
Published inAccounts of chemical research Vol. 35; no. 4; pp. 247 - 254
Main Authors Nelsen, Stephen F, Pladziewicz, Jack R
Format Journal Article
LanguageEnglish
Published United States American Chemical Society 01.04.2002
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Summary:Electron-transfer cross-reactions between neutral molecules and their radical cations spanning a wide range of structural type and intrinsic reactivity have been analyzed using classical Marcus theory. The principal factor found to govern intrinsic reactivity is the inner-shell bond reorganization energy. The HOMO−LUMO overlap of alkyl groups on reacting molecules is generally sufficient to provide facile electron transfer; however, a significant steric effect on this overlap is observed for hydrazines with alkyl groups larger than methyl.
Bibliography:istex:ABE863FEA14BE932D2A0B0E3B9E19790C30DD1EC
ark:/67375/TPS-MK0H4BHS-3
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ISSN:0001-4842
1520-4898
DOI:10.1021/ar0101077