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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.

Nickel(II) Dithiocarbamates with AsI3 and SbI3 as Mixed Ligands

Pastorek R., Kameníček J., Trávníček Z., Pavlíček M., Cvek B., Husárek J., Šindelář Z.

Polish Journal of Chemistry

2005

Vol. 79 / nr 4

637-644

Ni(II) dithiocarbamates with AsI3 or SbI3 as ligands of the composition [Ni(hmidtc)2(AsI3)] (1), [Ni(bzbutdtc)2(AsI3)] (2), [Ni(bzbutdtc)2(SbI3)]_2CHCl3 (3), [Ni(bz2dtc)2(AsI3)] (4), [Ni(bz2dtc)2(SbI3)]_CS2 (5), [Ni(hmidtc)2(AsI3)2]_CHCl3 (6), [Ni(hmidtc)2(SbI3)2] (7) and [Ni(cetdtc)2(AsI3)2] (8), (hmidtc = hexamethyleneiminedithiocarbamate, bzbutdtc = benzylbutyldithiocarbamate, bz2dtc = dibenzyldithiocarbamate, cetdtc = cyclohexylethyldithiocarbamate, dtc = S2CN-) have been synthesized. The complexes have been characterized by elemental analyses, thermal analysis, IR and UV/VIS spectroscopies, magnetochemical and conductivity measurements as square-pyramidal (1-5) and octahedral (6-8) complexes. X-ray analysis of [Ni(bz2dtc)2(AsI3)] and [Ni(bz2dtc)2(SbI3)]_CS2 confirmed square-pyramidal arrangement around nickel in both complexes with the NiS4As and NiS4Sb chromophore, respectively.