Neutral Gold Complexes with Tridentate SNS Thiosemicarbazide Ligands

Na­[AuCl4]·2H2O reacts with tridentate thiosemicarbazide ligands, H2L1, derived from N-[N′,N′-dialkylamino­(thiocarbonyl)]­benzimidoyl chloride and thiosemicarbazides under formation of air-stable, green [AuCl­(L1)] complexes. The organic ligands coordinate in a planar SNS coordination mode. Small amounts of gold­(I) complexes of the composition [AuCl­(L3)] are formed as side-products, where L3 is an S-bonded 5-diethylamino-3-phenyl-1-thiocarbamoyl-1,2,4-triazole. The formation of the triazole L3 can be explained by the oxidation of H2L1 to an intermediate thiatriazine L2 by Au3+, followed by a desulfurization reaction with ring contraction. The chloro ligands in the [AuCl­(L1)] complexes can readily be replaced by other monoanionic ligands such as SCN– or CN– giving [Au­(SCN)­(L1)] or [Au­(CN)­(L1)] complexes. The complexes described in this paper represent the first examples of fully characterized neutral Gold­(III) thiosemicarbazone complexes. All the [AuCl­(L1)] compounds present a remarkable cell growth inhibition against human MCF-7 breast cancer cells. However, systematic variation of the alkyl groups in the N(4)-position of the thiosemicarbazone building blocks as well as the replacement of the chloride by thiocyanate ligands do not considerably influence the biological activity. On the other hand, the reduction of AuIII to AuI leads to a considerable decrease of the cytotoxicity.