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A cyano-bridged coordination polymer, [Ni(NH3)6]2[{Ni(NH3)4}{Re12CS17(CN)6}] · 8H2O, has been synthesized by reaction between concentrated aqueous ammonia solution of NiCl2 and aqueous solution of K6[Re12CS17(CN)6]. The compound has been characterized by single crystal X-ray diffraction, IR-spectroscopy and EDS analysis. The compound adopts 1-D structure, which consists of anionic chains [{Ni(NH3)4}{Re12CS17(CN)6}] , discrete cations [Ni(NH3)6]2+ and crystal waters bonded together by hydrogen bonds. The influence of reagent concentrations on composition and structure of the resultant product has also been studied and discussed.

We report the direct facile high-temperature synthesis and investigation of heterometallic rhenium–molybdenum cluster K6[Re3Mo3S8(CN)4(CN)2/2] (1) with a new {Re3Mo3S8} core. Dissolution of polymeric compound 1 resulted in subsequent oxidation and formation of stable 23e paramagnetic anionic cluster complex [Re3Mo3S8(CN)6]6−.

An oxidation of cluster anion [Re(12)CS(17)(CN)(6)](6-) by H(2)O(2) in water has been investigated. It was shown that selective two-step oxidation of bridging μ(2)-S-ligands in trigonal prismatic unit {Re(3)(μ(6)-C)(μ(2)-S)(3)Re(3)} takes place. The first stage runs rapidly, whereas the speed of the second stage depends on intensity of ultraviolet irradiation of the reaction mixture. Each stage of the reaction is accompanied by a change in the solution's color. In the first stage of the oxidation, the cluster anion [Re(12)CS(14)(SO(2))(3)(CN)(6)](6-) is produced, in which all bridging S-ligands are turned into bridging SO(2)-ligands. The second stage of the oxidation leads to formation of the anion [Re(12)CS(14)(SO(2))(2)(SO(3))(CN)(6)](6-), in which one of the SO(2)-ligands underwent further oxidation forming the bridging SO(3)-ligand. Seven compounds containing these anions were synthesized and characterized by a set of different methods, elemental analyses, IR and UV/vis spectroscopy, and quantum-chemical calculations. Structures of some compounds based on similar cluster anions, [Cu(NH(3))(5)](3)[Re(12)CS(14)(SO(2))(3)(CN)(6)]·9.5H(2)O, [Ni(NH(3))(6)](3)[Re(12)CS(14)(SO(2))(3)(CN)(6)]·4H(2)O, and [Cu(NH(3))(5)](2.6)[Re(12)CS(14)(SO(2))(3)(CN)(6)](0.6)[{Re(12)CS(14)(SO(2))(2)(SO(3))(CN)(5)(μ-CN)}{Cu(NH(3))(4)}](0.4)·5H(2)O, were investigated by X-ray analysis of single crystals.