Picolylketone Thiosemicarbazones and S-Alkyldithiocarbazates

2-Picolylphenylketone S-benzyldithiocarbazate, 48, yielded paramagnetic [ Ni(48-H)A 2] (A = Cl, Br) and diamagnetic [Ni(48-H)I] [207]. All three compounds are non-electrolytes and the iodo complex is planar while the other two complexes involve sulfur bridging atoms and five-coordinate nickel(II) centers. All three complexes can be converted to monomeric, octahedral complexes by addition of pyridine, 2-picoline or quinoline. 

6-Lutidylphenylketone thiosemicarbazone, 38, and nickel(II) chloride, bromide, or iodide yield [Ni(38-H)2]A2 with NNS coordination based on infrared spectra [187]. All three complexes are electrolytes and the cations are dimeric with sulfur atoms acting as bridges interdimer interactions via sulfur are present. The electronic spectra suggest a nickel(Il) stereochemistry other than tetrahedral or octahedral for these paramagnetic complexes. 

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