Femtosecond dynamics of Norrish type-II reactions: Nonconcerted hydrogen-transfer and diradical intermediacy

Steven De Feyter, Wei-Guang Diau, Ahmed H. Zewail*

*Corresponding author for this work

Research output: Contribution to journalArticle

42 Scopus citations

Abstract

Norrish type-II and McLafferty rearrangements, which both involve an intramolecular transfer of a γ H atom, can be differentiated on the femtosecond time scale. The McLafferty rearrangement results in ion fragmentation of the parent ketone, whereas the Norrish type-II reaction leads to a diradical species, which then either cyclizes or fragments (see scheme). For Norrish type-II reactions, the reaction time for the transfer of the hydrogen atom is within 70-90 fs, and the lifetime of the diradical intermediate is in the range of 400-700 ps at the total energy studied.

Original languageEnglish
Pages (from-to)260-263
Number of pages4
JournalAngewandte Chemie - International Edition
Volume39
Issue number1
DOIs
StatePublished - 3 Jan 2000

Keywords

  • Density functional calculations
  • Diradicals
  • Femtochemistry
  • Hydrogen transfer
  • Norfish reactions

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