Spontaneous phosphorus-halogen bond cleavage in N-heterocyclic halogenophosphanes revisited: The case of P-Br and P-I bonds

Sebastian Burck, Dietrich Gudat, Martin Nieger, Zoltan Benkö, L. Nyulászi, D. Szieberth

Research output: Contribution to journalArticle

16 Citations (Scopus)

Abstract

P-bromo- and P-Iodo-substituted N-heterocyclic phosphanes (NHP) were synthesized by halogen exchange starting from the P-chloro compound and characterized by spectroscopic data and X-ray diffraction studies. Whereas the Br-NHP still forms a molecular crystal, the solid-state structure of the I-derivative consists of ion-pairs which assemble via secondary P⋯I interactions to form one-dimensional coordination polymers. Computational studies indicate that the bond dissociation is due to a combination of intramolecular stabilisation (aromatisation of the phosphenium cation formed) and intermolecular Lewis-acid/base interactions. Reaction of the I-NHP with I 2 proceeded under complete P-I bond cleavage to give an ionic phosphenium triiodide whose singlecrystal X-ray diffraction study revealed a unique supramolecular structure.

Original languageEnglish
Pages (from-to)245-252
Number of pages8
JournalZeitschrift fur Anorganische und Allgemeine Chemie
Volume635
Issue number2
DOIs
Publication statusPublished - Feb 2009

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phosphine
Halogens
Phosphorus
Molecular crystals
Aromatization
X ray diffraction
Lewis Acids
Cations
Polymers
Stabilization
Ions
Derivatives

Keywords

  • Bond dissociation
  • DFT studies
  • Halides
  • Phosphanes
  • X-ray diffraction

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Spontaneous phosphorus-halogen bond cleavage in N-heterocyclic halogenophosphanes revisited : The case of P-Br and P-I bonds. / Burck, Sebastian; Gudat, Dietrich; Nieger, Martin; Benkö, Zoltan; Nyulászi, L.; Szieberth, D.

In: Zeitschrift fur Anorganische und Allgemeine Chemie, Vol. 635, No. 2, 02.2009, p. 245-252.

Research output: Contribution to journalArticle

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AB - P-bromo- and P-Iodo-substituted N-heterocyclic phosphanes (NHP) were synthesized by halogen exchange starting from the P-chloro compound and characterized by spectroscopic data and X-ray diffraction studies. Whereas the Br-NHP still forms a molecular crystal, the solid-state structure of the I-derivative consists of ion-pairs which assemble via secondary P⋯I interactions to form one-dimensional coordination polymers. Computational studies indicate that the bond dissociation is due to a combination of intramolecular stabilisation (aromatisation of the phosphenium cation formed) and intermolecular Lewis-acid/base interactions. Reaction of the I-NHP with I 2 proceeded under complete P-I bond cleavage to give an ionic phosphenium triiodide whose singlecrystal X-ray diffraction study revealed a unique supramolecular structure.

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