Epimerization of cyclic vinylphosphirane complexes: The intermediacy of biradicals

Bing Wang, Charles H. Lake, Koop Lammertsma

Research output: Contribution to journalArticlepeer-review

39 Citations (Scopus)


The phosphinidene complex Ph-P-W(CO)5 reacts with cyclopentadiene, 1,3-cyclohexadiene, 1,3-cycloheptadiene, and 1,3-cyclooctadiene to give in each case isomeric mixtures of syn- and anti-vinylphosphiranes. With longer reaction times and/or higher reaction temperatures, the anti adducts isomerize to the syn adducts. These epimerizations are likely to proceed via biradical intermediates. Only the syn-vinylphosphirane of 1,3-cyclohexadiene undergoes a [1,3]-sigmatropic shift to yield a syn-phopholene. The dichotomy of biradical and concerted mechanisms is discussed in relationship with the analogous mechanism for the vinylcyclopropane → cyclopentene rearrangement.

Original languageEnglish
Pages (from-to)1690-1695
Number of pages6
JournalJournal of the American Chemical Society
Issue number7
Publication statusPublished - 21 Feb 1996
Externally publishedYes

ASJC Scopus subject areas

  • Catalysis
  • General Chemistry
  • Biochemistry
  • Colloid and Surface Chemistry


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