The kinetics of Z/E isomerization of methyl oleate catalyzed by photogenerated thiyl radicals

Chryssostomos Chatgilialoglu, Abdelouahid Samadi, Maurizio Guerra, Hanns Fischer

Research output: Contribution to journalArticlepeer-review

50 Citations (Scopus)

Abstract

The reaction of β-mercaptoethanol with methyl oleate in tert-butyl alcohol was investigated under photochemical conditions. The time-dependent Z/E isomerization of the unsaturated moiety as well as the thiol-adduct formation were analyzed on the basis of radical generation rates and established rate constants. This provides precise room-temperature rate constants for the reversible thiyl radical addition to both Z and E isomers. The rate constants for HOCH2CH2S. addition to the Z and E forms were found to be 1.6 × 105 and 2.9 × 105 M-1 s-1, respectively. For the β-elimination of the thiyl radical from the alkyl radical adduct, the rate constants were 1.7 × 107 and 1.6 × 108 s-1, the faster associated with the formation of the E isomer. DFT-BB1K calculations on 2-butene assign this large preference of fragmentation for the E isomer to a lower activation barrier for the formation of the E transition state from the equilibrium radical adduct structure.

Original languageEnglish
Pages (from-to)286-291
Number of pages6
JournalChemPhysChem
Volume6
Issue number2
DOIs
Publication statusPublished - Feb 2005
Externally publishedYes

Keywords

  • Density functional calculations
  • Isomerization
  • Kinetics
  • Photolysis
  • Radical reactions

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics
  • Physical and Theoretical Chemistry

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