Rhenium chalcogenides

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... 

Treatment of the rhenium sulfide chlorides with an excess of chlorine at temperatures above 450°C results in formation of ReCls 140). Reduction between 350 and 500°C gives binary rhenium chalcogenides 139,262). Action of water vapor on rhenium sulfide chlorides at 350-500°C produces oxysulfides 139). 

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). 

J.-C.P. Gabriel, K. Boubekeur, S. Uriel, O. Batail, Chemistry of hexanuclear rhenium chalcogenide clusters. Chem. Rev. 101 (2001) 2037. 

S.6.2.2 Cs6Re6Si2 - a ternary rhenium chalcogenide with two-dimensionally linked clusters... 

This approach has been fashioned in the pursuit of molecular rhenium chalcogenide clusters whose structures have not been accessible by conventional self-assembly techniques. The method, which has been termed cluster excision, involves the addition of a suitable ligand to the nonmolecular solid, such that the vacant sites on the metal centers will be occupied upon cleavage of the bridging interactions. Ligands that have been utilized in this approach include Cl and CN , affording molecular rhenium sulfide and selenide clusters (Equation (21)). This method also allows access to previously known structures under milder synthetic conditions ... 

In contrast to the synthetic accessibility of the above complexes using solution approaches, the synthesis of octahedral rhenium chalcogenide clusters requires the implementation of high temperature solid-state reactions, or the conversion of cluster-containing solids into soluble molecular species by the methods of cluster excision or dimensional reduction (see Section 7.2.2.1.8). While cluster excision has produced the mixed sulfide(selenide)-chloride clusters [Re6E4+ Clio 2 ] " ( = 1-3), the latter approach has led to the isolation of complexes with rhenium-chalcogenide cores [RegEgXg] - (E = S, Se X = C1, Br, I). 

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