Rhenium mixed-ligand complexes with S,N, S-tridentate thiosemicarbazone/thiosemicarbazide ligands

Rhenium(V) complexes containing tridentate thiosemicarbazones/thiosemicarbazides (H(2)L1) derived from N-[N', N'-dialkylamino(thiocarbonyl)] benzimidoyl chlorides with 4,4-dialkylthiosemicarbazides have been synthesized by ligand-exchange reactions starting from [ReOCl(L1)]. The chlorido ligand of [ReOCl-(L1)] (4) is readily replaced and reactions with ammonium thiocyanate or potassium cyanide give [ReO-(NCS)(L1)] (6) and [ReO(CN)(L1)] (7), respectively. The reaction of (NBu4)[ReOCl4] with H(2)L1 and two equivalents of ammonium thiocyanate, however, gives in a one-pot reaction [ReO(NCS)(2)(HL1)] (8), in which the pro-ligand H(2)L1 is only singly deprotonated. An oxo-bridged, dimeric nitridorhenium(V) compound of the composition [{ReN(HL1)}(2)O] (11) is obtained from a reaction of (NBu4)[ReOCl4], H(2)L1 and sodium azide. The six-coordinate complexes [ReO(L1)(Ph(2)btu)] (12), where HPh2btu is N, N-diphenyl-N'-benzoylthiourea, can be obtained by treatment of [ReOCl(L1)] with HPh(2)btu in the presence of NEt3. Studies of the antiproliferative effects of the [ReOX(L1)] system (X = Cl-, NCS- or CN-) on breast cancer cells show that the lability of a monodentate ligand seems to play a key role in the cytotoxic activity of the metal complexes, while the substitution of this ligand by the chelating ligand Ph(2)btu(-) completely terminates the cytotoxicity.