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Three routes to nickel(II) salicylaldehyde 4-phenyl and 4-methylthiosemicarbazonato complexes: mechanochemical, electrochemical and conventional approach

In the synthesis of Ni(II) salicylaldehyde 4-phenyl and 4-methyl-thiosemicarbazonato complexes conventional, electrochemical and mechanochemical routes were applied and compared. Polynuclear tetrahedral [Ni(sal 4-Metsc)]n (1) and mononuclear square planar [Ni(sal 4-Phtsc)(H2sal 4-Phtsc)]$ CH3OH (2) were obtained by the conventional method. The electrochemical synthesis proved to be a simple and efficient route for the synthesis of brownish-red single crystals of square planar (2) and polycrystalline green octahedral [Ni(Hsal 4-Metsc)2]$(3) complexes, while the liquid-assisted mechanochemical synthesis was a fast route for the synthesis of green octahedral [Ni(Hsal 4- Metsc)2]$(3) and [Ni(Hsal 4-Phtsc)2]$(4). The advantages and disadvantages of all used synthetic methods were discussed. The characterization of square planar (2) and two octahedral complexes (3) and (4) was performed by X-ray diffraction methods, infrared and NMR spectroscopy. In addition quantum chemical calculations were performed for CS (conformer which enables O–H/S intramolecular hydrogen bond formation in 2-hydroxyaryl Schiff base thiosemicarbazones) and SC (conformer with the thiocarbonyl group turned away from O–H/N intramolecular hydrogen bond) forms of both ligands and in each case the CS conformer was lower in energy.

Ni(II) salicylaldehyde 4-phenyl and 4-methyl-thiosemicarbazonato complexes; conventional; electrochemical and mechanochemical synthesis

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