Fused tricyclic phosphiranes - Analysis of phosphorus chemical shielding

Erik P.A. Couzijn, Andreas W. Ehlers, J. Chris Slootweg, Marius Schakel, Steffen Krill, Martin Lutz, Anthony L. Spek, Koop Lammertsma

Research output: Contribution to journalArticlepeer-review

13 Citations (Scopus)

Abstract

1,2-Addition of transient W(CO)5-complexed phosphinidenes exo to hexamethyl Dewar benzene affords the novel 3-phosphatricyclo[3.2.0.0 2,4]hept-6-ene complexes. The fused tricyclic phosphiranes are obtained as both the Z and the thermally less stable E isomers, the 31PNMR chemical shifts of which differ by about 60 ppm. A computational investigation shows that the phosphorus pyramidalization and the presence of the γ double bond are responsible for this effect. The semiquantitative results contribute to a more systematic understanding of the structural influences on 31P chemical shieldings. The congested double bond of the Z isomer can be epoxidized with m-chloroperbenzoic acid (MCPBA) to afford a fused tetracyclic P,O bis-adduct.

Original languageEnglish
Pages (from-to)1499-1507
Number of pages9
JournalChemistry - A European Journal
Volume14
Issue number5
DOIs
Publication statusPublished - 8 Feb 2008
Externally publishedYes

Keywords

  • Density functional calculations
  • Fused-ring systems
  • NMR spectroscopy
  • Phosphorus heterocycles
  • Ring strain

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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