ISSN print edition: 0366-6352
ISSN electronic edition: 1336-9075
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Isomerism of octahedral thiosemicarbazide nickel(II) complexes

A. Sirota, T. Šramko, and J. Gažo

Department of Inorganic Chemistry, Slovak Technical University, SSO 37 Bratislava


Abstract: Solid nickel(II) complexes with thiosemicarbazide, CH5N3S (tsc), of the type [Ni(tsc)3]X2 were prepared, X being NO3 (monohydrate and anhydrous), CI (anhydrous), Br-(anhydrous), I- (dihydrate and anhydrous   α and ß isomer), and СlO4 (dihydrate and anhydrous). Their spectral, magnetic, and thermal properties were investigated. The above complexes are paramagnetic and show electronic absorption spectra typical of octahedral nickel(II) complexes. Thiosemicarbazide molecules were proved to be bidentate ligands, forming NiN3S3 environment around the central atom. Infrared absorption spectra allowed to separate the complexes under investigatio into two groups: 1. nitrates, Perchlorates, and iodides (dihydrate and anhydrous a isomer), 2. anhydrous chloride, bromide, and iodide (ß isomer). Differences found in electronic absorption spectra were in good agreement with those observed in infrared spectra. Splitting of absorption bands as well as the crystal structure analysis results known for [Ni(tsc)3](NO3)2 . H2O and [Ni(tsc)3](N03)2, make it possible to come to the conclusion that the complexes of the first group have 1,2,3-arrangement of ligands (cis), while those of the second group are most probably trans isomers with 1,2,6-arrangement. The anhydrous α  and ß forms of iodide (green or blue, respectively) are considered to be geometrical isomers. Method for preparation of both isomers and their mutual interconversions are given in the present paper. It has been found that the ß isomer is thermodynamically more stable.

Full paper in Portable Document Format: 301a90.pdf


Chemical Papers 30 (1) 90–99 (1976)

Wednesday, March 29, 2023

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