Novel thiosemicarbazonato complexes of gold(III) have been prepared from reactions of [Au(damp-C¹,N)Cl₂ (damp- = 2-(N,N-dimethylaminomethyl)phenyl) or [NBu₄][AuCl₄] with 2-pyridineformamide thiosemicarbazones (HL). The thiosemicarbazones deprotonate and coordinate as mononegative, tridentate NNS ligands to gold to give [Au(Hdamp-C¹)(L)]Cl₂ or [AuCl(L)]Cl complexes. The organometallic damp⁻ ligand is protonated during the reactions and the Au–N bond is cleaved. The [AuCl(L)]⁺ cations represent the first gold(III) complexes with thiourea derivatives which are not stabilised by an additional organometallic ligand. Reactions of [NBu₄][AuX₄] (X = Cl, Br) with diphenylthiocarbazone (dithizone) result in reduction of the metal and the formation of gold(I) complexes of the composition [AuX(SCN₄-3,4-Ph₂)] where SCN₄-3,4-Ph₂ is 3,4-diphenyltetrazole thione which is formed from cyclisation of dithizone.

Similar reactions of 2,6-dipicolinoylbis(N,N-diethylthiourea) (H₂L^a) with: (i) Ni(NO₃)₂·6H₂O, (ii) a mixture of Ni(NO₃)₂·6H₂O and AgNO₃, (iii) a mixture of Ni(OAc)₂·4H₂O and PrCl₃·7H₂O and (iv) a mixture of Ni(OAc)₂·4H₂O and BaCl₂·2H₂O give the binuclear complex [Ni₂(L^a)₂(MeOH)(H₂O)], the polymeric compound [NiAg₂(L^a)₂]_∞, and the heterobimetallic complexes [Ni₂Pr(L^a)₂(OAc)₃] and [Ni₂Ba(L^a)₃], respectively. The obtained assemblies can be used for the build up of supramolecular polymers by means of weak and medium intermolecular interactions. Two prototype examples of such compounds, which are derived from the trinuclear complexes of the types [M^II ₂Ln^III(L)₂(OAc)₃] and [M^II ₂Ba(L)₃], are described with the compounds {[Cu^II ₂Dy^III(L^a)₂(p-O₂C-C₆H₄-CO₂)(MeOH)₄]Cl}_∞ and [Mn^II ₂Ba(MeOH)(L^b)₃]_∞, H₂L^b = 2,6-dipicolinoylbis(N,N-morpholinoylthiourea).