Variations in the chain structure of cationic (phosphine)gold(I) dialkyldithiophosphate complexes

Max Preisenberger, Annette Schier, Hubert Schmidbaur

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Treatment of dithiophosphoric acid diesters (RO)2P(S)SH with appropriate quantities of tris[(phosphine)gold(I)]oxonium tetrafluoroborates {[(R′3P)Au]3O}+ BF4- in dichloromethane gives di-or trinuclear complexes of the types {(RO)2P[SAu(PR′3)]2/3}+/2+ (2) BF4- as colourless, crystalline salts. As determined by single crystal X-ray diffraction studies, in the 1:2 complexes (with R = R′ = Me and R′ = Et, R = Ph and o-Tol), each gold atom is attached to a different sulfur atom, but with short intracationic Au-Au contacts. These cations are associated to form strings through intermolecular Au-Au contacts in the first case (R = Et), but through additional Au-S contacts in the second (R = Ph). For R = o-Tol, the cations are not associated at all owing to steric hindrance. This result is indicative of very small energy differences between the two modes of association. The 1:3 complexes are fluxional in solution and show virtually equivalent R3PAu groups in the NMR spectra at 20°C, but at low temperature non-equivalent ligands can be distinguished as shown previously for analogous dithiophosphinate derivatives.

Original languageEnglish
Pages (from-to)781-787
Number of pages7
JournalZeitschrift fur Naturforschung - Section B Journal of Chemical Sciences
Issue number8
StatePublished - Aug 1998
Externally publishedYes


  • Dithiophosphinates
  • Gold Complexes
  • Phosphinates
  • Thiophosphinates


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