The IR spectra of dithiocarbamic acids alkali salts and Ni(II), Cu(II), and Zn(II) chelates are studied in the region of 3 800-200 cm-1. The results are correlated with X-ray diffraction data. The position of the absorption bands of the dithiocarbamates is affected mainly by the nature of the central atom and the character of the group bonded to the nitrogen atom, influencing the charge density distribution at the C-N and M-S bonds. The structure of the coordination sphere affects the M-S and C_N bonds, which, however, manifests itself only in the IR band shape, the ν(C-N), ν(C-S), and ν(M-S) band position remaining unaltered.
This work deals with the synthesis of dithiocarbamate chelates of Cu(II) and Zn(II) with ligands derived from dimethyl-, diethyl-, dipropyl-, dibutyl- and methylisopropylamine, piperidine and morpholine and the electronic spectra of these substances in the UV and visible regions. The absorption spectra of the cupric (and zinc(II)) chelates contain a single analytically important band around 270 (260) nm, assigned to the π-π* transition within the ligand, that is affected by the substituent on the nitrogen atom and the solvent polarity. Lengthening of the alkyl chain leads to increased intensity of the bands and a red shift of their λmax; increased solvent polarity leads to increased intensity of the bands and a blue shift.
The synthesis and electronic spectra of the chelates of nickel(II) dithiocarbamates with ligands derived from dimethyl-, diethyl-, dipropyl-, dibutyl-, dipentyl-, dihexyl-, diheptyl-, dioctyl-, diisopropyl-, methylisopropylamine, piperidine, morpholine and piperazine are discussed. The absorption bands in the chelate spectra around 220 and 245 nm are assigned to absorption localized primarily in the S-C=S and N-C=S ligand groups. The analytically most important band with λmax around 330 nm assigned to M-L charge transfer is affected by alkyl substituents on the nitrogen atom and by the solvent polarity. The lengthening of the alkyl chain causes the increase in the intensity of the band and red-shift of its λmax; the increase of the polarity of the solvent leads to an increase in the band intensity and a blue shift.
The report gives synthesis and UV spectra of a series of alkali and ammonium salts of the dithiocarbamic acids derived from dimethyl-, diethyl-, dipropyl-, dibutyl-, dipentyl-, dihexyl-, diheptyl-, dioctyl-, diisopropyl-, diisobutyl-, methylisopropylamine, piperidine, morpholine, piperazine and pyrrolidine. The absorption bands due to transitions localized in the groups CSS (λmax ~ 260 nm) and NCS (λmax ~ 280 nm) show a red shift with increasing length of the alkyl chain. Increasing polarity of solvent causes, with some of the compounds, a small red shift of λmax of the band due to CSS group, but it causes a considerable blue shift of λmax of the band due to NCS group in all the studied compounds. The absorption band near 207 nm is ascribed to the carbon disulphide produced by decomposition of the dithiocarbamates.
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