Some Tris[(triorganophosphine)gold(I)]‐oxonium and ‐Organoimonium Tetrafluoroborates with Bulky Substituents

Andreas Kolb, Peter Bissinger, H. Schmidbaur

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37 Scopus citations


Tris{[tri(2‐methylphenyl)phosphine]gold(I)}‐, tris{[tri(2,4,6‐trimethylphenyl)phosphine]gold(I)}‐ and tris{[tri(cyclohexyl)phosphine]gold(I)}‐oxonium tetra‐fluoroborate (1−3) have been prepared from the corresponding (phosphine)gold(I) chlorides, silver oxide, and sodium tetrafluoroborate in acetone. These oxonium salts are excellent aurating agents for primary amines. Thus in the reaction with 1, t‐butylamine tBuNH2 and aniline PhNH2 are readily converted into the trinuclear imino complexes {[(2‐MeC6H4)3P]Au}3NtBu+BF4 (4) and {[(2‐MeC6H4)3P]Au}3NPh+BF 4− (5) in high yields. With 3, both aniline and 8‐amino‐quinoline also give the trinuclear complexes, i.e. {[(c‐C6H11)3P]Au}3 NPh+BF 4− (6) and {[(c‐C6H11)3P]Au}3N(C9H6N)+BF 4− (7). Auration of aniline with the most sterically hindered reagent 2 yields only the binuclear complex {[2,4,6‐Me3C6H2)3P] · Au}2N(Ph)H+BF 4− (8). The reagents 1−3 and the Products 4–8 have been characterized by analytical and NMR spectroscopic data, and the crystal structures of compounds 4 and 6 have been determined by single crystal x‐ray diffraction. In the cations of 4, a triangle of gold atoms with short Au — Au contacts [3.036(1), 3.107(1), and 3.214(1) Å] forms a steep pyramid with the nitrogen atom, in which the angles AuNAu are all much smaller than the tetrahedral standard of 109.7°: 94.8(4), 98.1(4), and 103.0(4)°. This triangular Au3 unit is staggered relative to the three methyl groups of the tBu substituent at nitrogen. The results for 6 are similar [Au — Au: 3.037(1), 3.071(1), and 3.222(1) Å; AuNAu: 95.3(3), 96.5(3), and 103.6(3)°]. Variable temperature NMR studies of compounds 3 and 8 show hindered rotation of the mesityl groups about the PC bonds of the ligands originating from the steric congestion within each tertiary phosphine.

Original languageEnglish
Pages (from-to)1580-1588
Number of pages9
JournalZeitschrift fur Anorganische und Allgemeine Chemie
Issue number9
StatePublished - Sep 1993
Externally publishedYes


  • (Triorganophosphine)gold(I) Complexes
  • Gold(I) Complexes
  • Tris[(triorganophosphine)gold(I)]imonium Salts
  • Tris[(triorganophosphine)gold(I)]oxonium Salts


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