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The cluster complex (Me4N)K7[{Re4(µ3-CCN)4}(CN)12]·10H2O (I) is synthesized by the high-temperature reaction of ReI3 with KCN and subsequent recrystallization from an aqueous solution with the addition of Me4NI. The anion of complex I contains ligands µ3-CCN3– stabilized due to coordination to the triangular faces of the {Re4} tetrahedral metal cluster. It is shown for [Ni(Еn)2]2+ as an example that the µ3-CCN3– ligands are ambidentate and can interact with transition metal cations similarly to the terminal CN groups, affording the coordination polymer [Ni(En)2(NH3)2][{Ni(En)2}3{Re4(µ3-CCN)4}(CN)12]·7.5H2O (II). The structures of complexes I and II are determined by X-ray diffraction analysis (CIF file ССDС nos. 2057450 (I) and 2057451 (II)).

By a high-temperature reaction of rhenium(III) iodide and red phosphorus with an excess of sodium cyanide followed by recrystallization from an aqueous solution a new tetrahedral [{Re4(PO)4}(CN)12]8– anionic cluster complex is obtained. It is isolated as a salt of the composition Na8[{Re4(PO)4}(CN)12] 18H2O·MeOH. The structure of the obtained compound is determined by X-ray crystallography. The compound crystallizes in the monoclinic crystal system, P21/n space group, unit cell parameters a = 26.826(3) A, b = 11.4975(12) A, c = 29.141(3) A, β = 97.879(2)°, V = 8903.2(16) A3, Z = 8.

A new method is proposed for the synthesis of the octahedral rhenium chalcocyanide cluster complexes [{Re6(μ3-Q)8}(CN)6]4– (Q = S, Se, Te) using rhenium(IV) oxide as the starting compound. Among the synthesized compounds, the anhydrous cluster salt K4[{Re6Se8}(CN)6] is characterized by X-ray diffraction analysis for the first time. The crystals are orthorhombic, space group Pbcn; a = 13.1386(13), b = 11.4941(8), c = 17.2990(16) A, Z = 4, V = 2612.4(4) A3 (CIF file IСSD no. 434320). The crystal structure of K4[{Re6Se8}(CN)6] represents a framework type packing based on the K+ cations coordinated by the cyanide groups of the cluster anions [{Re6Se8}(CN)6]4–.