Displacement of the weakly co-ordinating tetrahydrothiophene (tht) ligand in [AuX(tht)], [Au(tht)₂]ClO₄, or [Au(PPh₃)(tht)]ClO₄(X = Cl or C₆F₅) by heterocyclic thiones HL (HL = C₃H₅NS₂, C₄H₄N₂S, C₅H₅NS, C₇H₅NS₂, or C₇H₆N₂S), leads to the formation of neutral or cationic complexes of the types [AuX(HL)], [Au(HL)₂]ClO₄, or [Au(PPh₃)(HL)]ClO₄. For gold(III) complexes the tht ligand cannot be displaced but [Au(C₆F₅)₃(OEt₂)] reacts with HL to give neutral complexes [AuR₃(HL)]. Deprotonation of the NH unit in the cationic complexes leads to neutral monomeric complexes and since the deprotonated N atom is now a donor, binuclear complexes can be prepared by displacement of a weakly co-ordinating ligand from other suitable complexes. The structure of [Au(HL)₂]ClO₄(HL = C₅H₅NS) has been established by X-ray crystallography [space group P, a= 9.609(3), b= 15.024(6), c= 16.712(7)Å, α= 97.52(4), β= 104.17(2), γ= 104.76(2)°, and R′= 0.045 for 5 499 unique observed reflections]. The cations are arranged in a way that is unprecedented for gold(I) compounds. Five of the six cations in the cell are linked by short Au ⋯ Au contacts (3.3 Å) and the sixth cation is monomeric.