Preparation and crystal structure of bis(isocyanide)gold(I) bis(phenylene-1,2-dithiolato)aurates(III)

The reaction of (isocyanide)gold(I) chlorides [(RNC)AuCl, R = ^tBu, ^cHex] with phenylene-1,2-dithiol and sodium methoxide (molar ratio 2:1:2) in methanol / dichloromethane leads to the formation of deep green mixed-valent salts [(RNC)₂Au]⁺[Au(S₂C₆H ₄)₂]^- in ca. 35% yield. As determined by single crystal X-ray diffraction methods, the two compounds have entirely different supramolecular structures. For R = ^tBu stacked planar anions and rod-like cations form alternating layers, while for R = ^cHex alternating cations and anions are arranged in chains with long S- -Au contacts [3.422 Å].