Transition metal complexes with thiosemicarbazide-based ligands. XLII. Bis(S-methylisothiosemicarbazido-N1, N4)bis(pyrazole-N2)-nickel(II) diiodide.

In the title compound, [Ni(C(2)H(7)N(3)S)(2)(C(3)H(4)N(2))(2)]I(2), the Ni(II) ion assumes a centrosymmetric distorted octahedral geometry. The two molecules of S-methylisothiosemicarbazide are coordinated as bidentate ligands via the terminal N atoms, forming five-membered chelate rings. The I atoms are approximately in the equatorial plane of the chelate rings at a similar distance from both. The five-membered chelate rings are almost planar and exhibit flattened envelope conformations. There is a weak intermolecular interaction between the lone pair of electrons of the S atom and the center of the pyrazole ring.

Mixed cobalt(III) complexes with aromatic amino acids and diamine. Part II. Synthesis and configuration of (1,2-diaminoethane)bis(L-tyrosinato)cobalt(III)complex diastereomers. The crystal structure of the delta-C1-cis(O) diastereomer.

In the reaction of trans-[CoCl2(en)2]+ with L-tyrosine all six theoretically possible diastereomers of the (1,2-diaminoethane)bis(L-tyrosinato)cobalt(III) complex were formed. The following five were isolated: gamma-trans(O); and gamma- and delta-C2-cis(O) and gamma- and delta-C1-cis(O) diastereomers, while the delta-trans(O) diastereomer was only detected in the corresponding eluate. Separation of the obtained diastereomers was performed by chromatography on a Dowex 1 x 4 column. Characterization of the isolated diastereomers was carried out by means of elemental analysis, electronic absorption, circular dichroic, 1H and 13C NMR spectra, and by x-ray crystal structure analysis in the case of the delta-C1-cis(O) diastereomer. We established the general rule of preference of diasteromers formation in complexes of [Co(L-aa)2diamine]+ (L-aa = L-amino acid anion; diamine = 1,2-diaminoethane or 1,3-diaminopropane) type.