The pyridine-carboxamide ligand PhNHC(O)2-C 5 H 4 N reacts with Na + [AuCl 4 ] − either by cation exchange, to give [PhNHC(O)2-C 5 H 4 NH][AuCl 4 ], or by ligand substitution to give [AuCl 2 (κ 2 -N,N′-PhNC(O)2-C 5 H 4 N)]. Similar reactions with bis(pyridine-carboxamide) ligands gave complexes [AuCl 2 (κ 2 -N,N′-RNC(O)2-C 5 H 4 N)], with R=(CH 2 ) 3 NHC(O)2-C 5 H 4 N or 2-C 6 H 4 NHC(O)2-C 5 H 4 N, in which the ligands are bidentate, but no complexes with tetradentate ligands could be isolated. The complex [AuCl 2 (κ 2 -N,N′-PhNC(O)2-C 5 H 4 N)] in methanol solution is an efficient catalyst for oxidative cyanation of PhNMe 2 to give PhMeNCH 2 CN, and it is proposed that the catalysis involves gold(I), gold(II) and gold(III) intermediates.