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 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.
Nelsen
Stephen F
SF
Department of Chemistry, University of Wisconsin-Madison, Wisconsin 53706-1396, USA.
Pladziewicz
Jack R
JR