Replenishment in the Family of Rhenium Chalcobromides; Synthesis and Structure of Molecular {Re 4 S 4 }Br 8 (TeBr 2 ) 4 , Dimeric [{Re 4 S 4 }Br 8 (TeBr 2 ) 3 ] 2 , and Polymeric {Re 4 S 4 }Br 8 Compounds Based on the {Re 4 S 4 } 8+ Tetrahedral Cluster Core.

We have obtained three new rhenium(IV) chalcobromides belonging to the homologous series {Re 4 S 4 }Br 8 (TeBr 2 ) n ( n = 0, 3, 4): a molecular complex {Re 4 S 4 }Br 8 (TeBr 2 ) 4 ( 1 ), a dimeric complex [{Re 4 S 4 }(TeBr 2 ) 3 Br 7 (μ-Br)] 2 ( 2 ), and a two-dimensional (2D) polymeric compound {Re 4 S 4 }Br 8 ( 3 ). Compound 1 is isotypic to the already known {Re 4 Te 4 }(TeBr 2 ) 4 Br 8 , while 2 and 3 exhibit a new type of binding of tetrahedral clusters via μ-Br bridges. Compounds were characterized by X-ray single-crystal diffraction, X-ray powder diffraction, and thermal and elemental analyses. In compound 2 , two tetrahedral cluster cores {Re 4 S 4 } 8+ are linked together forming a dimer through two Re-μ-Br-Re bridges. Calculations of the electron localization function (ELF) showed that there is no covalent interaction between rhenium atoms of neighboring clusters. In compound 3 , each rhenium atom of the {Re 4 S 4 } 8+ core is coordinated by three Br ligands: one terminal Br and two bridging μ-Br ligands. As a result, eight bridging bromine atoms link {Re 4 S 4 } 8+ cluster cores into goffered layers. {Re 4 S 4 }Br 8 is the new stable rhenium(IV) thiobromide, the first discovered in the Re-S-Br system, along with the already known octahedral rhenium(III) thiobromides Re 6 S 4+ x Br 10-2 x ( x = 0-4).