Barrierless electron transfer bond fragmentation reactions

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

Research output: Contribution to journalArticle

31 Scopus citations

Abstract

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
Volume126
Issue number43
DOIs
StatePublished - Nov 3 2004

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ASJC Scopus subject areas

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

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