The [B12 H12](2-) anion shows an extensive substitutional chemistry based on its three-dimensional aromaticity. The replacement of functional groups can be attained by electrophilically induced substitution caused by Brønsted or Lewis acidic electrophiles (e.g. Pt(2+)). Until now, it was impossible to structurally characterize a metal-substituted [B12 H12](2-) cage. When an aqueous solution containing both Bi(3+) cations and [B12 H12](2-) anions was heated, the charge-neutral bismuth undecahydro-closo-dodecaborane BiB12 H11 was obtained, representing a new class of metalated [B12 H12](2-) clusters. The title compound was characterized by single-crystal X-ray diffraction and NMR spectroscopic methods. Compared to the typical B-H bond, the short B-Bi single bond (230 pm) exhibits inverted polarity.
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