Treatment of the (isocyanide)gold(I) species LAuCl (L t BuNC, 2,6-Me 2 C 6 H 3 NC) with 4-mercaptobenzoic acid in the presence of NaOMe yields the complexes [Au(4-SC 6 H 4 CO 2 H)L] in good yield. Reaction of LAuCl with 2-HSQn (Qn quinoline) and 2-HSPy (Py pyridine) under the same conditions provides the thiolato compounds [Au(2-SQn)L] and [Au(2-SPy)L], respectively. A structural investigation of the pyridylthiolato compound revealed chains of molecules with alternating medium and long AuÀAu interactions. Treatment of this compound with HBF 4 results in the cationic species [Au(2-HSPy)(2,6-Me 2 C 6 H 3 NC)] as the BF 4
À salt. The same product is obtained on reaction of [AuCl(2,6-Me 2 C 6 H 3 NC)] with AgOTf followed by HSPy. Treatment of the gold(I) halide compounds LAuCl (L t BuNC, 2,6-Me 2 C 6 H 3 NC) with potassium 1,3,4thiadiazole-2,5-dithiolate (KSSSK) leads to the isolation of dinuclear thiolatogold complexes [(AuL) 2 (SSS)]. These products go on to form insoluble polymers through loss of isocyanide on standing in solution. A single crystal of [{Au( t BuNC)} 2 (SSS)] was obtained and the subsequent structural analysis revealed one of the most complicated networks known based solely on aurophilic interactions. A good comparison to the soft Sdonation of the thiolato ligands was provided by the synthesis of a number of nitratogold(I)complexes with the anion bound through the hard O-donor. Reaction of i PrNC and CyNC with Au(tht)Cl provided the complexes [AuCl( i PrNC)] and [AuCl(CyNC)], respectively. These compounds were found to yield the respective nitrato species [Au(NO 3 ) i PrNC)] and [(Au(NO 3 )(CyNC)] on treatment with AgNO 3 . The nitrato complexes yielded single crystals enabling a structural investigation to be carried out. While [Au(NO 3 )(CyNC)] has a more conventional structure with dimers aligned into strings with alternating short and long aurophilic bonding, [Au(NO 3 )( i PrNC)] has a unique structure based on strings of alternating, corner-sharing Au 6 and Au 8 units with short AuÀAu contacts in edge-sharing Au 3 triangles.
2 ) Crystallographic data (excluding structure factors) for the structures reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as deposition No. CCDC 172317 ± 172320.