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Synthesis, Characterization and Kinetics of Metal Complexes Containing Dithiocarbamate and Polypyridine

Rafat R., Siddigi K., Siddiqi M.

Polish Journal of Chemistry

2007

Vol. 81, nr 3

313-326

Complexes of the type [M(L)(ddtc)2], where M = Mn(II), Co(II), Ni(II), Cu(II) and Zn(II), L = 2,2'-bipyridine or 1,10-phenanthroline and ddtc = diethyldithiocarbamate, have been synthesized and characterized by elemental analyses, IR, electronic, EPR, 1H NMR spectral data, magnetic moment and conductivity measurements. The electrical conductivity of the complexes indicated them to be non-electrolyte in nitrobenzene. The spectroscopic evidences suggest that the complexes have an octahedral environment around the metal ion. Plot of log [Delta/Delta-Delta m] against time was linear suggesting first order kinetics of nuceophilic substitution of [Ni(bpy)(ddtc)2] by chloride ion in nitrobenzene. The results show that the rate of substitution is independent of the concentration of the nucleophile and depends only on the first power of the concentration of the complex.

An Anionic Moiety, MCl2- 4 (M=copper, zinc, cadmium and mercury) Stabilized by Bis(diethylenetriamine)copper(II) Cation

Siddiqi K., Rafat F., Siddiqi M., Lutfullah, Chebude Y.

Polish Journal of Chemistry

2004

Vol.78 /nr 11-12

2047-2053

Bimetallic complexes of the type [Cu(dien)2][MCl4], where M = Cu(II), Zn(II), Cd(II) and Hg(II), were prepared by reacting bis(diethylenetriamine)copper(II) dichloride with copper, zinc, cadmium and mercury dichlorides in ethanol. They have been characterized by elemental analyses, IR, electronic and EPR spectra, magnetic moment, TGAand conductivity measurements. Electrical conductivity of all the complexes indicated them to be 1:1 electrolyte in DMF and that the copper(II) ion is paramagnetic, maintaining its octahedral geometry, while metal ions in the anionic moiety of the complexes achieve their usual tetrahedral environment. An augmented magnetic moment has been observed in the [Cu(dien)2][CuCl4] complex, which is attributed to the ferromagnetic effect. From the EPR spectra, the Cu-Cu distance (rjk) has been found to be larger in [Cu(dien)2][CdCl4] than in [Cu(dien)2][CuCl4]. The TGAof [Cu(dien)2][CuCl4] showed the decomposition of various fragments between 226 to 1000 graduate C.