Gold Complexes with Thiosemicarbazones and Phosohine Thiolates

Square-planar AuIII complexes are isoelectronic to PtII compounds which are frequently used for cancer therapy. Recently, cancerostatic properties have also been reported for dichloro[2-(dimethylamino-methyl)phenyl-C1,N]gold(III), [Au(damp-C1,N)Cl2] (I) [1], although the mechanism of cytotoxic action may well be different. This encourages us to study the ligand exchange chemistry of this type of compound more in detail.
We have synthesized and structurally characterized a series of AuIII complexes with bi- and tridentate thiosemicarbazones as well as with chelating phosphine thiol ligands which surprisingly stabilize gold in its formal oxidation state "+3".
Reactions of (I) with thiosemicarbazones result in a cleavage of the Au-N bond and protonation of the liberated dimethylamino group. Airstable, zwitterionic compounds are formed. The thiosemicarbazones co-ordinate as deprotonated chelate ligands substituting Cl-. Fig. 1 illustrates an example with the bidentate vanillinethiosemicarbazone. Remaining Cl- ligands can be replaced by further ligand exchange reactions, e.g. with thiolates.