Barrierless electron transfer bond fragmentation reactions

Edward D. Lorance, Wolfgang H. Kramer, Ian Gould

Research output: Contribution to journalArticlepeer-review

36 Scopus citations


The ultrafast N-O bond fragmentation in a series of N-methoxypyridyl radicals, formed by one-electron reduction of the corresponding N-methoxypyridiniums, has been investigated as potentially barrierless electron-transfer-initiated chemical reactions. A model for the reaction involving the electronic and geometric factors that control the shape of the potential energy surface for the reaction is described. On the basis of this model, molecular structural features appropriate for ultrafast reactivity are proposed. Femtosecond kinetic measurements on these reactions are consistent with a kinetic definition of an essentially barrierless reaction, i.e., that the lifetime of the radical is a few vibrational periods of the fragmenting bond, for the p-methoxy-N-methoxypyridyl radical.

Original languageEnglish (US)
Pages (from-to)14071-14078
Number of pages8
JournalJournal of the American Chemical Society
Issue number43
StatePublished - Nov 3 2004

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry


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