Intramolecular Phosphine-Phosphine Donor-Acceptor Complexes

Piotr Wawrzyniak, Amy Fuller, Alexandra Martha Zoya Slawin, Petr Kilian

Research output: Contribution to journalArticlepeer-review

43 Citations (Scopus)

Abstract

The reaction of 5-diphenoxyphosphanyl-6-diisopropylphosphinoacenaphthene 12 with chlorotrimethylsilane unexpectedly gave a phosphonium-phosphine compound 13, containing the structural motif of four phosphorus atoms connected in a chain. To explain the mechanism of this complex transformation, a proposed intermediate 5-dichlorophosphino-6-diisopropylphosphinoacenaphthene 14 was synthesized by an alternative method. The two (formally) phosphine environments in 14 form an intramolecular donor-acceptor (phosphonium-phosphoranide) complex, stable at room temperature in the solid state and as a solution in certain solvents. A P-31 NMR mechanistic study showed that, despite the presence of a rigid acenaphthene backbone, 14 is unstable in the presence of nucleophiles and disproportionates into 13 and other phosphorus containing products. Both 13 and 14 have been crystallographically characterized.

Original languageEnglish
Pages (from-to)2500-2506
Number of pages7
JournalInorganic Chemistry
Volume48
Issue number6
DOIs
Publication statusPublished - 16 Mar 2009

Keywords

  • PHOSPHORUS
  • CHLORIDES
  • SKELETON
  • ELEMENTS
  • SYSTEM
  • CATION

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