Effect of diverse solvents on the composition and structure of mixed-ligand nickel(II) dithiocarbamates: [NiX(ndtc)(PPh3)]

A series of square-planar nickel(II) benzylpiperazine–dithiocarbamato (bpdtc; 1–4) and thiomorpholine–dithiocarbamato (tmdtc; 5–8) complexes of the composition [NiX(ndtc)(PPh3)] (X symbolizes Cl for 1 and 5, Br for 2 and 6, I for 3 and 7, or NCS for 4 and 8) was prepared and thoroughly characterized by elemental analysis, UV–Vis, IR and NMR spectroscopy, mass spectrometry, molar conductivity and magnetochemical measurements, and by single-crystal X-ray analysis (for complex 1). The solution behaviour study of selected representatives (1, 4, 5 and 8) in various solvents (acetone, acetonitrile, methanol (MeOH), N,N′-dimethylformamide (DMF), chloroform, nitromethane, dimethyl sulfoxide (DMSO), MeOH/water mixture (1:1 v/v)) by a combination of NMR and UV–Vis spectroscopy, mass spectrometry and single-crystal X-ray analysis showed that the complexes decompose back to the synthetic precursors, involving the [Ni(ndtc)2] species, in DMF and DMSO, while they dissolve without a change in their composition in the remaining solvents.

Graphical abstractDistorted square-planar nickel(II) dithiocarbamato complexes of the composition [NiX(ndtc)(PPh3)] (X = Cl, Br, I or NCS) were prepared and thoroughly characterized. Their solution behaviours in various organic solvents were described and the results were compared with the solid state properties.Figure optionsDownload full-size imageDownload as PowerPoint slide