Addition of a phosphinidene complex to C=N bonds: P-ylides, azaphosphiridines, and 1,3-dipolar cycloadditions

Mark J.M. Vlaar, Pieter Valkier, Frans J.J. De Kanter, Marius Schakel, Andreas W. Ehlers, Anthony L. Spek, Martin Lutz, Koop Lammertsma

Research output: Contribution to journalArticlepeer-review

25 Citations (Scopus)


The terminal phosphinidene complex PhPW(CO)5 adds to the imine bond of PhHC=N-Ph to give 3-membered ring azaphosphiridines, which undergo ring-expansion with an additional imine to yield a set of four isomeric five-membered ring diazaphospholanes. Treatment with the diimines PhHC=N(CH2)n-N=CHPh (n=2,3,4) results instead - in all three cases - in only a single isomer of the (CH2)n, bridged diazaphospholane. For n = 2 or 3, this aminal group is easily hydrolyzed to afford new 6- and 7-membered ring heterocycles. No intermediate azaphosphiridine complex is observed during the addition reaction to the diimines. B3LYP/6-31G* calculations on an unsubstituted, uncomplexed system suggest that the initially formed P,N-ylide of the H2C=N-(CH)2-N=CH2 diimine both kinetically and thermodynamically favors an intramolecular 1,3-dipolar cyclo-addition over an imine insertion into the CPN ring of an intermediate azaphosphiridine. Single-crystal X-ray structures for the (CH2)2-bridged azaphospholane complex and the HCl adduct of the 7-membered hydrolysis product are presented.

Original languageEnglish
Pages (from-to)3551-3557
Number of pages7
JournalChemistry - A European Journal
Issue number16
Publication statusPublished - 17 Aug 2001
Externally publishedYes


  • Complexed phosphinidene cycloaddition
  • Density functional calculations
  • Heterocycles
  • Ylides

ASJC Scopus subject areas

  • Catalysis
  • General Chemistry
  • Organic Chemistry


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