Volume 49, Nº 1 (2023)

The reaction of binuclear zinc dipropyldithiocarbamate [Zn2{S2CN(C3H7)2}4] with an AuCl3/2 М HCl solution is studied. The double ionic complex [Au{S2CN(C3H7)2}2]2[ZnCl4] (I) is identified as the main species of gold(III) binding in the heterogeneous system under study and is characterized by 13С and 15N CP-MAS NMR spectroscopy. Single crystals of heterovalent compound [Au{S2CN(C3H7)2}2]2[AuCl4][AuCl2] (II) are sampled as a by-product. The crystal and supramolecular structures of complexes I and II are determined by the direct XRD method (CIF files CCDC nos. 2159171 and 2159170, respectively). The self-organization of the complex pseudopolymeric structures of compounds I and II are shown to be due to the binding of ionic structural units by secondary nonvalent interactions Au⋅⋅⋅S and S⋅⋅⋅Cl and hydrogen bonds C–H⋅⋅⋅Cl. The thermal behavior of the complexes is studied by simultaneous thermal analysis (STA), and the quantitative regeneration of bound gold (I and II) with the partial transformation of released ZnCl2 to ZnS (I) is found.

The reactions of TpReO(SnC3H7)2 (Tp = tris(pyrazolyl)borate anion) with acetonitrile complexes PdCl2(MeCN)2 and PtI2(MeCN)2 in toluene solutions resulted in the formation of new heterometallic rhenium complexes TpReO(µ-SnC3H7)2MX2 (MX2 = PdCl2 (I), MX2 = PtI2 (II)). A similar complex TpReO(µ-SnC3H7)2PdI2 (III) was formed either on treatment of I with NaI in dichloromethane or in the reaction of TpReO(SnC3H7)2 with a suspension of PdI2 in toluene. Complexes I–III were characterized by IR and NMR spectroscopy and by X-ray diffraction (CCDC nos. 2172225–2172227).

A series of mono- and bimetallic cation-anionic complexes based on the [PtPy4]2+ cation with different single-charge anions of carboxylic acids (RCOO–) is synthesized and structurally characterized. A synthetic approach to the preparation of tetrapyridineplatinum complexes [PtPy4]2+ soluble in polar solvents from available reagents is developed. The reaction of tetrapyridineplatinum dichloride [PtPy4](Cl)2 with silver acetate or trifluoroacetate affords compounds [PtPy4](OOCMe)2·6H2O (I) and [PtPy4](OOCCF3)2· 2H2O (II) in the form of crystalline hydrates (CIF files CCDC nos. 2161100 and 2161101, respectively) in high yields. Other carboxylates can be prepared by the treatment of compound I with an excess of a stronger acid, for example, trifluoroacetic acid, with the formation of the corresponding complex trifluoroacetate [PtPy4](OOCCF3)2·4CF3COOH (IIa) (CIF file CCDC no. 2161102). Another method consists of the displacement of acetic acid with an excess of a lowly volatile acid, for example, pivalic acid, when [PtPy4](Piv)2· 5HPiv (III) is formed from the acid melt, and solvatomorph [PtPy4](Piv)2·4HPiv·3C6H12 (IIIa) (CIF files CCDC nos. 2161103 and 2161104, respectively) is formed in a cyclohexane medium. Heteroanionic heterometallic complex [PtPy4](OOCFc)(OOCMe) (IV) (CIF file CCDC no. 2161105) is shown to be formed by the reaction of complex I with ferrocenecarboxylic acid under mild conditions.