Olefin Reactivities toward the Ph-P-W(CO)5 Phosphinidene

Jui Te Hung, Suh Wan Yang, Pooran Chand, Gary M. Gray, Koop Lammertsma

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30 Citations (Scopus)


Phosphinidene complex Ph-P-W(CO)5 (2), generated from the appropriate phosphanorbornadiene complex 1, reacts with olefins to give the expected phosphiranes. The relative olefin reactivity toward 2 in toluene at 55 °C is tetramethylethylene (0.2), trimethylethylene (0.8), isobutylene (2-4), cis-2-butene (1.0), trans-2-butene (0.3), and 1-butene (0.2). The modest stereoselectivity of the phosphinidene addition reactions is reflected in the synlanti-phosphirane product ratios of several olefins and results form opposing steric and electronic influences. For cis-2-butene the synlanti ratio is 0.25 and the X-ray structure of the anit-isomer was determined. The surprising lack of olefin selectivity is compared with the olefin reactivities of various carbenes and particularly that of isopropylidene. The phosphinidene-olefin additions behave analogously to the carbene cyclopropanations and suggest the importance of entropie factors in the thermodynamically controlled reactions.

Original languageEnglish
Pages (from-to)10966-10971
Number of pages6
JournalJournal of the American Chemical Society
Issue number24
Publication statusPublished - 1 Nov 1994
Externally publishedYes

ASJC Scopus subject areas

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


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