Ionothermal Syntheses, Crystal Structures, and Chemical Bonding of the Rhodium‐Centered Clusters [RhBi 9 ] 4+ and [(RhBi 7 )I 8 ]

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The first filled Bi 9 5+ polycation was isolated in the form of [RhBi 9 ](AlCl 4 ) 4 crystals by dissolution of the solid precursor Bi 12– x Rh X 13– x in the Lewis‐acidic ionic liquid [BMIm]Cl·3.6AlCl 3 (BMIm = 1‐butyl‐3‐methylimidazolium) at 140 °C. In the monoclinic crystal structure [ P 2 1 / n, a = 1217.5(2) pm, b = 1741.6(3) pm, c = 5085.7(7) pm, β = 90.117(8)°], the almost spherical [RhBi 9 ] 4+ polycations (approximate D 3 h symmetry; Rh–Bi 276 ± 3 pm) show pronounced orientational disorder. Shiny black needles of Bi 7 RhI 8 were obtained from the reaction of rhodium, bismuth, and BiI 3 in the ionic liquid [BMIm]Cl · 1.3AlCl 3 at 200 °C. Bi 7 RhI 8 [ P 2 1 / n, a = 943.10(1) pm, b = 1582.40(1) pm, c = 1645.40(1) pm, β = 95.48(1)°] is isostructural to Bi 7 RhBr 8 and consists of molecular clusters [(RhBi 7 )I 8 ]. The rhodium atom centers a pentagonal bipyramid of bismuth atoms, and the two apical bismuth atoms are in square‐planar coordination of iodide ions. DFT‐based calculations indicate strong bismuth‐rhodium bonding with predominantly covalent character for both clusters. The electronic structure of the Bi 9 5+ cage is notably modified by this interaction, but the characteristic bonding features of the host cluster with the D 3 h configuration are still maintained. In Bi 7 RhI 8 , on the other hand, bonding is dictated by the spatial distribution of mutually repelling iodine atoms, and the Bi–Rh bonding is highly polar.