Transition metal ion complexes of theS-methyldithiocarbazate prepared from 2-acetylpyridine

Summary Metal ion complexes of 2-acetylpyridineS-methyldithiocarbazate, HNNS, have been prepared and spectrally characterised. Preparations in EtOH yield complexes in which the deprotonated ligand, NNS, is complexedvia its pyridyl nitrogen, azomethine nitrogen, and thione sulphur. The stoichiometries are: [M(NNS)₂]X (M=Fe³⁺, Co³⁺ and X=ClO₄^–, [FeCl₄]^–, BF₄^–, 1/2 [CoCl₄]^2– and 1/2 [CoBr₄]^2–), [M(NNS)X] (M=Ni²⁺, Cu²⁺ and X=Cl^–, Br^–), [Cu(NNS)H₂O]BF₄ and Ni(HNNS)(NNS)F(EtOH)]BF₄. The spectral (i.e., i.r., u.v.-vis.-n.i.r. and e.s.r.) and physical properties of these complexes are compared to those of theS-methyldithiocarbazates of 2-formylpyridine and 2-acetylpyridineN-oxide, as well as the related thiosemicarbazones prepared from 2-acetylpyridine. Thermal studies of the nickel(II) complexes indicate that the nature of thermal decomposition of coordinated NNS is different from that of HNNS.