Synthesis and conformational studies of palladium(II) complexes containing [Ph2P(O)NP(E)Ph2]- (E = S or Se)

Alexandra Martha Zoya Slawin, MB Smith, John Derek Woollins

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22 Citations (Scopus)

Abstract

The ligands [Ph2P(O)NP(E)Ph-2](-) (E = S I: E = Se II) can readily be complexed to a range of palladium(II) starting materials affording new six-membered Pd-O-P-N-P-E palladacycles. Hence ligand substitution reaction of the chloride complexes [PdCl2(bipy)] (bipy - 2,2'-bipyridine), [{Pd(mu-Cl)(L-L)}(2)] (HL-L = C9H13N or C12H13N), [{Pd(mu Cl)Cl(PMe2Ph)}(2)] or [PdCl2(PR3)(2)] [PR3 = PPh3; 2PR(3) = Ph2PCH2CH2PPh2 or cis-Ph2PCH = CHPPh2] with either I (or II) in thf or CH3OH gave [Pd{Ph2P(O)NP(E)Ph-2-O,E}(bipy)]PF6, [Pd{Ph2P(O)NP(E)Ph-2-O,E} (L-L)], [Pd{Ph2P(O)NP(E)Ph-2-O,E}Cl(PMe2Ph)] or [Pd{Ph2P(O)NP(E)Ph-2-O,E} (PR3)(2)]PF6 in good yields. All compounds described have been characterised by a combination of multinuclear NMR [P-31{H-1} and H-1] and IR spectroscopy and microanalysis. The molecular structures of five complexes containing the selenium ligand II have been determined by single-crystal X-ray crystallography. Three different ring conformations were observed, a pseudo-butterfly, hinge and in the case of: all three PR, complexes, pseudo-boat conformations. Within the Pd-O-P-N-P-Se rings there is evidence for x-electron delocalisation. (C) 1998 Elsevier Science Ltd. All rights reserved.

Original languageEnglish
Pages (from-to)4465-4473
Number of pages9
JournalPolyhedron
Volume17
Publication statusPublished - 1998

Keywords

  • metallacycles
  • palladium
  • ligands
  • X-ray
  • RAY CRYSTAL-STRUCTURE
  • MOLECULAR-STRUCTURE
  • TETRAPHENYL IMIDODIPHOSPHATE
  • PLATINUM(II) COMPLEXES
  • SULFUR
  • PH(2)PNHP(O)PH(2)
  • COORDINATION
  • DERIVATIVES
  • REACTIVITY
  • COMPOUND

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