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

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}₃N^tBu⁺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.