Use of molecular scaffolding for the stabilization of an intramolecular dative PIII-PV system

Petr Kilian, Douglas Philp, Alexandra M.Z. Slawin, J. Derek Woollins*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

41 Scopus citations


The reaction of NapP2S4 (1; Nap = naphthalene-1,8-diyl) with chlorine gas gave [Nap(PCl2)(PCl4)] (2), displaying a rare σ4P-σ6P bonding interaction. An X-ray structure analysis confirmed the PCl5-like, P-P bond containing phosphonium-phosphoride structure of 2 in the crystal, which was also found in solution at low temperature. At ambient and higher temperatures, dynamic behaviour on the NMR time-scale was observed, which was assigned to interchange of the ionic phosphonium-phosphoride form 2 and the molecular bis(phosphorane) Nap(PCl3)2 form 3, rather than to the ionic phosphonium salt-phosphorane form [Nap(PCl3)(PCl2)][Cl] 4. Electronic structure calculations were performed at the B3LYP/6-31G(d,p) level of theory on structures 2 and 3; structure 3 was located as a local minimum on the potential energy surface, 15 kcal·mol-1 higher in energy than structure 2. The crystal structure and calculated P-P distances are 2.34 2,34 and 2.31 Å for 2 and 3, respectively. An activation energy of 19.7 kcal·mol-1 was found for the transition state structure by coordinate driving calculations; the line-shape analysis of variable temperature 31P{1H} NMR spectra gave an activation energy of 14.4 kcal·mol-1.

Original languageEnglish (US)
Pages (from-to)249-254
Number of pages6
JournalEuropean Journal of Inorganic Chemistry
Issue number2
StatePublished - Jan 2003


  • Neighbouring-group effects
  • Phosphorus heterocycles
  • Phosphorus-phosphorus bond
  • Strained molecules

ASJC Scopus subject areas

  • Inorganic Chemistry


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