Photochemical generation of a primary vinyl cation from (E)-bromostyrene: Mechanisms of formation and reaction

R. Gronheid, H. Zuilhof, M.G. Hellings

Research output: Contribution to journalArticleAcademicpeer-review

17 Citations (Scopus)

Abstract

The photochemistry of (E)-bromostyrene was investigated to determine the nature of the product-forming intermediates and to clarify the mechanism of formation of vinylic cations and vinylic radicals. Both a cation- and a radical-derived product are formed, and the ionic origin of the former product is demonstrated by significant scrambling of the label, starting from specifically deuterated (E)-bromostyrene. MO calculations show that the isolated incipient primary vinyl cation is not a metastable species, but that specific interaction with a counterion in combination with a polar environment makes it metastable. The effects of variation of the wavelength of irradiation, solvent polarity, temperature, and isotopic substitution all agree with a mechanism of direct heterolytic C-Br bond cleavage producing an ion pair followed by formation of a radical pair via electron transfer. The vinylic cation is proposed to stem directly from the indirectly populated lowest excited singlet state of bromostyrene with an energy of activation of 6.7 kcal/mol. Branching between proton loss and electron transfer in the resulting ion pair determines the ratio of cation- to radical-derived product. The E/Z-isomerization occurs in a separate process and does not involve C-Br bond cleavage
Original languageEnglish
Pages (from-to)3205-3215
JournalJournal of Organic Chemistry
Volume68
Issue number8
DOIs
Publication statusPublished - 2003

Keywords

  • ion-pairs
  • alkyl-halides
  • triarylvinyl cations
  • photolysis
  • bromides
  • electron
  • substitution
  • carbocations
  • solvolysis
  • radicals

Fingerprint Dive into the research topics of 'Photochemical generation of a primary vinyl cation from (E)-bromostyrene: Mechanisms of formation and reaction'. Together they form a unique fingerprint.

Cite this