Application of the Marcus Cross Relation to Hydrogen Atom Transfer Reactions

Science  21 Dec 2001:
Vol. 294, Issue 5551, pp. 2524-2526
DOI: 10.1126/science.1066130

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The transfer of a hydrogen atom—a proton and an electron—is a fundamental process in chemistry and biology. A variety of hydrogen atom transfer reactions, involving iron complexes, phenols, hydroxylamines, tBuOOH, toluene, and related radicals, are shown to follow the Marcus cross relation. Thus, the Marcus theory formalism based on ground-state energetics and self-exchange rates, originally developed for electron transfer processes, is also valuable for hydrogen atom transfer. Compounds that undergo slow proton transfer (C–H bonds) or slow electron transfer (cobalt complexes) also undergo slow hydrogen atom transfer. Limitations of this approach are also discussed.

  • * Present address: Department of Chemistry, University of California at Berkeley, Berkeley, CA 94720, USA.

  • Present address: Changwon National University, 9 Sarim-dong, Changwon, Kyungnam 641-773, South Korea.

  • To whom correspondence should be addressed. E-mail: mayer{at}

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