Rhenium chalcogenide halides

All of the known rhenium chalcogenide halides are stable in air. With the exception of RegSgCU, they are insoluble in water, acids, and the common organic solvents. They dissolve readily in hot, 50% KOH (263, 264). Re2S3Cl4 is soluble in water, and ethanol, but insoluble in nonpolar organic solvents. With acids, alkalis, or hot water, hydrolytic decomposition takes place. Alkaline solutions can be oxidized to produce perrhenate compounds. 

Preparative Routes and Experimental Conditions for the Formation OF Rhenium Chalcogenide Halides... 

The structures of the rhenium chalcogenide halides have not been studied. X-Ray powder data were collected, in order to prove the homogeneity of the compounds 140, 263, 264, 353). 

Much of the interest in clusters of this type arises from their structural similarity to the fundamental structural element of the superconducting Chevrel phases M MogEg (M = Pb, Sn, Cu, etc.) and more recently discovered rhenium halco halide phases. Although these solid-state compounds are known only for Mo and Re, molecular MgEgLg clusters of Zr, V, Cr, Mo, W, Re, Fe, and Co have been reported (Table 2). The lone examples of octahedral zirconium- and vanadium-chalcogenide clusters are unique in that they also possess interstitial O and S atoms, respectively. Evidence for interstitial FI atoms in the clusters [Cr6Eg(PEt3)g] (E = S, Se) has been presented. ... 

Solid-state cluster chemistry is dominated by octahedral (M 5L8)L6 and (MsLi2)L units which are the focus of this paper. These two cluster types are different in the way the metal octahedral core is surrounded by the ligands. In (MsLg)L6-type clusters (Fig. 6.1a), typical for molybdenum and rhenium halides, chalcogenides, and chalcohalides, eight innei hgands (L ) cap the octahedron faces and six outer ligands (L ) are located in the apical positions [9]. For metals with a smaller number of valence electrons, the (M6L i2)L -type clusters... 

The alkali metal rhenium- and technetium chalcogenide clusters described in Section 5.6 are also octahedral.These clusters have M6Es units with eight face-capping anions on the octahedral faces in contrast to the niobium halide or oxide clusters. The A4M6S14 (A = alkali metal, M — Re, Tc), Cs6Rc6Si2, and... 

A comparable series of bridged structure types is found in rhenium 6-8 clusters, e.g., Ba2(Re0S0S3-3g 2) (Bronger Miessen, 1982). Further versatility develops with the use of both chalcogenide and halide which provide the novel layered Re0Se0Cl2 (Re0Se 4Se " 4/2Se 4/2Cp2)... 

---