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The reaction of Bi, BiCl3, and CuCl in the ionic liquid [BMIm]Cl⋅4 AlCl3 (BMIm=1‐n‐butyl‐3‐methylimidazolium) at 180 °C yielded air‐sensitive shiny black crystals of (CuBi8)[AlCl4]2[Al2Cl7] and (CuBi8)[AlCl4]3. For both compounds X‐ray diffraction on single crystals revealed monoclinic structures that contain the intermetalloid cluster (CuBi8)3+. It is the first pure bismuth cluster with a 3d metal...
The intermetalloid cluster (CuBi8)3+ combines two elements that usually avoid mutual bonding. It forms from bismuth, BiCl3, and CuCl under ionothermal conditions in a Lewis acidic ionic liquid that contains an excess of AlCl3. One of the [AlCl4]− counterions directly coordinates to the copper atom. The multicenter bonding in the (CuBi8)3+ cage, revealed by quantum‐chemical analysis, matches its description...
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