Kinetics of reductive N-O bond fragmentation

The role of a conical intersection

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

Research output: Contribution to journalArticle

66 Citations (Scopus)

Abstract

N-alkoxyheterocycles can act as powerful one-electron acceptors in photochemical electrontransfer reactions. One-electron reduction of these species results in formation of a radical that undergoes N-O bond fragmentation to form an alkoxy radical and a neutral heterocycle. The kinetics of this N-O bond fragmentation reaction have been determined for a series of radicals with varying substituents and extents of delocalization. Rate constants varying over 7 orders of magnitude are obtained. A reaction potential energy surface is described that involves avoidance of a conical intersection. A molecular basis for the variation of the reaction rate constant with radical structure is given in terms of the relationship between the energies of the important molecular orbitals and the reaction potential energy surface. Ab initio and density functional electronic structure calculations provide support for the proposed reaction energy surface.

Original languageEnglish (US)
Pages (from-to)15225-15238
Number of pages14
JournalJournal of the American Chemical Society
Volume124
Issue number51
DOIs
StatePublished - Dec 25 2002

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Potential energy surfaces
Rate constants
Electrons
Kinetics
Photochemical reactions
Molecular orbitals
Interfacial energy
Reaction rates
Electronic structure
alkoxyl radical

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Kinetics of reductive N-O bond fragmentation : The role of a conical intersection. / Lorance, Edward D.; Kramer, Wolfgang H.; Gould, Ian.

In: Journal of the American Chemical Society, Vol. 124, No. 51, 25.12.2002, p. 15225-15238.

Research output: Contribution to journalArticle

Lorance, Edward D. ; Kramer, Wolfgang H. ; Gould, Ian. / Kinetics of reductive N-O bond fragmentation : The role of a conical intersection. In: Journal of the American Chemical Society. 2002 ; Vol. 124, No. 51. pp. 15225-15238.
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