Intermolecular electron transfer reactivity determined from cross-rate studies.
2002
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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