Abstract
2-Acetylpyridine N(4)-dihexyl- and N(4)-dicyclohexylthiosemicarbazone, HAc4DHex and HAc4DCHex, respectively, and FeIII, CoII, CoIII, NiII, CuII and ZnII complexes have been prepared and characterized by molar conductivities, magnetic susceptibilities and spectroscopic techniques. For many of the complexes, loss of the N(2)H hydrogen occurs, and the ligands coordinate to the metal centres as NNS monoanionic, tridentate ligands, e.g., [M(NNS)X] (M = CoII, NiII, CuII, NNS = Ac4DHex or Ac4DCHex and X = Cl or Br), [Fe(NNS)2]ClO4, [Co(NNS)2]BF4, [Cu(NNS)NO3] and [Zn(NNS)OAc]. ZnII ion is also chelated by neutral ligands in [Zn(HNNS)X2] (X = Cl, Br). In addition, [Ni(Ac4DHex)-(HAc4DHex)]X (X = BF4, ClO4) and [Ni(HAc4DCHex)2]-(BF4)2 are reported where the neutral thiosemicarbazone is coordinated via the pyridyl nitrogen, azomethine nitrogen and thione sulfur. Crystal structure determinations of HAc4DCHex and [Cu(Ac4DHex)Br] show the former to contain the bifurcated hydrogen bonded form and the latter to be planar with no significant interaction between neighbouring centres.
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