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Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of ChalcogenidoplumbatesII or IV
Published on: December 29, 2016
Coordination Variability through Inner-Outer-Sphere Chloride Exchange in Complex Heterometallic Clusters
S M Gayomi K Samarakoon1, Spencer R Watts1, George D Tisdale1
1Department of Chemistry, Louisiana State University, Baton Rouge, Louisiana 70803, United States.
Abstract:
Five novel heterometallic bismuth-bearing cluster salts within two structural families, monoclinic P21/c α-[M2Bi14Cl4][TrCl4]4 and triclinic P1̅ [M2Bi14Cl2][AlCl4]6 (M = Ru, Os; Tr = Al, Ga), have been discovered via Lewis acidic ionic liquid (LAIL)-assisted synthesis at 180 °C. At the center of both structures is the binuclear inorganic [(Bi5)M(Bi4Clx)M(Bi5)](4,6)+ cluster cation (x = 2, 4), where the inner-sphere chloride content within the median [Bi4Clx] ring determines the charge of the unit, its symmetry, and the number of outer-sphere [AlCl4]- anions required for charge balance. Detailed characterization of the structural relationships, coupled with a comprehensive study of the electronic structure and bonding, indicates the basal-basal Bi-Bi strengthening, apical-basal weakening within [Bi5]+ upon chloride loss, and only minor influence of the transition metal origin on the symmetry of the cluster, besides relatively stronger Os-Os interactions of the two cluster types. These findings indicate inner-outer-sphere chloride exchange in LAILs, controlled by the amount of AlCl3, and periodic substitutions as viable approaches to control symmetry, bonding, and interconversion in Bi-rich clusters.
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