C-C bond insertion of a complexed phosphinidene into 1,6-methano[10] annulene

Rosa E. Bulo, Linda Trion, Andreas W. Ehlers, Fransiscus J.J. De Kanter, Marins Schakel, Martin Lutz, Anthony L. Spek, Koop Lammertsma

Research output: Contribution to journalArticlepeer-review

15 Citations (Scopus)


Reaction of electrophilic phosphinidene complex [MePW(CO)5] with 1,6-methano-[10]annulene results in the sole formation of the isomeric C-C insertion products 6c (main) and 6d (minor). The single-crystal X-ray structure of the complexed 1,7-methano-3-phospha[11]annulene (6c) shows a syn-W(CO) 5 group at the exo bent phosphorus. The structure displays C-C bond alternation without bonding between the bridgehead carbon atoms. Density functional theory calculations indicate 6c to result from a concerted disrotatory ring opening of an undetected tricyclic exo-syn phosphirane intermediate. The endo-anti phosphirane cannot undergo ring expansion, due to the high barrier that is associated with an intramolecular antara-antara retro Diels-Alder reaction. The stabilizing effect of transition-metal coordination is discussed.

Original languageEnglish
Pages (from-to)5332-5337
Number of pages6
JournalChemistry - A European Journal
Issue number21
Publication statusPublished - 25 Oct 2004
Externally publishedYes


  • Annulenes
  • Density functional calculations
  • Electrophilic substitution
  • Phosphorus
  • Tungsten

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry


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