Methylene-azaphosphirane as a reactive intermediate

J. Chris Slootweg, Mark J.M. Vlaar, Danielle J. Vugts, Tanja Eichelsheim, Winita Merhai, Frans J.J. De Kanter, Marius Schakel, Andreas W. Ehlers, Martin Lutz, Anthony L. Spek, Koop Lammertsma

Research output: Contribution to journalArticlepeer-review

10 Citations (Scopus)


Reaction of the transient phosphinidene complexes R-P= W(CO)5 with N-substituted-diphenyl-ketenimines leads unexpectedly to the novel 2-aminophosphindoles, as confirmed by an X-ray crystal structure determined for one of the derivatives. Experimental evidence for a methylene-azaphosphirane intermediate was found by using the iron-complexed phosphinidene iPr 2N-P=Fe(CO)4, which affords the 2-aminophosphindole together with the novel methylene-2,3-dihydro-1H-benzo[1,3]azaphosphole. Analysis of the reaction pathways with DFT indicates that the initially formed methylene-azaphosphirane yields both phosphorus heterocycles by way of a [1,5]- or [1,3]-sigmatropic shift, respectively, followed by a H-shift. Strain underlies both rearrangements, which causes these remarkably selective conversions that can be tuned by changing the substituents.

Original languageEnglish
Pages (from-to)4808-4818
Number of pages11
JournalChemistry - A European Journal
Issue number16
Publication statusPublished - 5 Aug 2005
Externally publishedYes


  • Density functional calculations
  • Heterocycles
  • Methylene cyclopropane
  • Reaction mechanisms
  • Reactive intermediates

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry


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