Synthesis and characterisation of bis(diphenylphosphino)-amine complexes of platinum(II)

P BHATTACHARYYA, R N SHEPPARD, A M Z SLAWIN, D J WILLIAMS, J D WOOLLINS

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33 Citations (Scopus)

Abstract

The complexes [PtCl(PR3)(dppa)]Cl (PR3 = PMe3, PMe2Ph, PMePh2, PBu3n, PPh3 or PEt3) have been prepared by the reaction of bis(diphenylphosphino)amine,dppa (Ph2PNHPPh2), with cis-[PtCl2(PR3)2] in CH2Cl2. With [PtCl2(dppe)] (dppe = Ph2PCH2CH2PPh2), [Pt(dppe)(dppa)]Cl2 is formed. The PEt3 complex undergoes halide exchange with excess of Br- or I- to give [PtX(PEt3)(dppa)]X. The compound [PtCl2(dppa)] has been prepared from [PtCl2(cod)] (cod = cycloocta-1,5-diene). The products have been characterised by P-31-{H-1}, Pt-195 and H-1 NMR spectroscopy, microanalysis and FAB mass spectrometry. The molecular structures of [PtCl(PMe2Ph)(dppa)]Cl.1.5CHCl3, [PtCl(PBu3n)(dppa)]Cl and [Pt(dppe)(dppa)]Cl2.CH2Cl2 have been determined by single-crystal X-ray diffraction, and show a square-planar arrangement around the platinum with the dppa acting as a chelate through both phosphorus atoms to give a four-membered PtP2N ring whose geometry is distinctly different from that of the deprotonated systems. All of the dppa NH groups hydrogen bond to an adjacent Cl- in the solid state.

Original languageEnglish
Pages (from-to)2393-2400
Number of pages8
JournalJournal of the Chemical Society, Dalton Transactions
Issue number15
DOIs
Publication statusPublished - 7 Aug 1993

Keywords

  • X = CL
  • MOLECULAR-STRUCTURE
  • CRYSTAL-STRUCTURE
  • POLYFUNCTIONAL MOLECULES
  • OXIDATIVE ADDITION
  • CHEMISTRY
  • REACTIVITY
  • PHOSPHINES
  • LIGANDS
  • DERIVATIVES

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