Silylimido and Disilylamido Groups as Clustering Centers for (Phosphane)gold(I) Units: Aurated Silylammonium Cations

Klaus Angermaier, Hubert Schmidbaur

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27 Scopus citations

Abstract

The reaction of hexamethyldisilazane with tris[(phosphane)‐aurio(I)]oxonium tetrafluoroborates affords the corresponding trinuclear μ3‐trimethylsilylimido compounds of the type {[(R3P)Au]3NSiMe3}+ BF−4 (1a‐f). With (triphenylsilyl)amine and the oxonium reagents the analogous series of Ph3Si derivatives (2a‐f) is formed (R = Me, Et, iPr; R3 = Ph2Me; R = Ph, o‐Tol). The Et3P‐based oxonium salt and (Me3Si)2NH give the dinuclear μ‐trimethylsilylamido complex {[(Et3P)Au]2N(SiMe3)2)2}+ BF−4 (3) as the main product. The crystal and molecular structures of complexes 2a, 2e, and 3 were determined. The trinuclear cations have a pseudo‐tetrahedral structure with small Au‐N‐Au angles and short Au‐Au distances for the SiNAu3 units. The Ph3SiN units in 2a and 2e are capping triangles of gold atoms, while in the cation of 3 the (Me3Si)2N unit is bridging a pair of gold atoms. In the 31P‐ and 14N‐NMR spectra of compounds 1 and 2 (except for 1f and 21) the coupling J(31P,14N) is observed. This coupling is temperature‐dependent, owing to changes in the relaxation characteristics in solution at low temperature. The decomposition of compounds 1 and 2 leads to the formation of pentanudear dications {[(R3P)Au]5N}2+ for R = Me, Ph.

Original languageEnglish
Pages (from-to)817-822
Number of pages6
JournalChemische Berichte
Volume128
Issue number8
DOIs
StatePublished - Aug 1995
Externally publishedYes

Keywords

  • μ ‐Silylimido‐tris[(phosphane)gold] cations
  • μ‐Disilylamido‐bis[(phosphane)gold] cations

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