Intermolecular Electron Transfer Reactivity Determined from Cross-Rate Studies
Accounts of Chemical Research2002Vol. 35(4), pp. 247–254
Citations Over TimeTop 10% of 2002 papers
Abstract
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.
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