Oxidation of N, N-di-n-butyldithiocarbamato (buzdtc) complexes of Cum, NiOI), ZnOI), Cd(I1) and Hg(II) is reported. Oxidation of Ni(bu2dtc)z with Clz, Brz, or of NiXz (X = CI, Br, Nos) with N,N,N',N'-tetra-n-butylthiuram disulfide (burtds) gives complexes of composition mi(buzdtc)3]X. These compounds are diamagnetic and dissolve in nitrobenzene as 1 : 1 electrolytes, their W spectra resemble that of the iso-electronic Co(buzdtc)s. The experimental data are in accord witli the assumption that in these compounds N i O (low spin d6) is surrounded by 6 S atoms in octahedral symmetry. The analogous selenium compound tris(N, N-di-n-butyldiselenocarbamato) nickelQV) bromide, having the same properties as the thio compounds, can also be prepared. Oxidation of Cu(buzdtc) with Clz or Brz yields paramagnetic products with the composition CuXa(buzdtc), in which Cu also has the formal oxidation number + 4, but the structure of these compounds is still obscure. Oxidation of Zn(buzdtc)z and the corresponding Cd and Hg compounds yields products, the analysis of which suggests the composition MXz(buzdtc)z (M = Zn, Cd or Hg, X = Br or I), but infrared studies indicate that the dithiocarbamato ligands of the starting substances are oxidized to buctds, which in the reaction products is coordinated to the metal in its normal oxidation state + 2.

No abstract

No abstract

In order to find characteristic differences between symmetrically and unsymmetrically bonded N,N‐dialkyldithiocarbamates, their IR and 1H NMR spectra have been examined. The IR data firmly underline a previously reported infrared criterion which makes it possible to distinguish the two types of bonding. In the spectra of the unsymmetrical N,N‐diethyldithiocarbamates a band at 1000 cm−1 is assigned to the CS stretching mode. Although the rotation around the S2C‐NR2, bond in several dithiocarbamato complexes will be strongly hindered at low temperatures, no splitting of the NMR signals of the N‐alkyl groups could be observed. This may be attributed to an extremely small difference in magnetic environment of the N‐alkyl moieties in the rotamers.

No abstract