Six-vertex closo-TeB5 Cl5 (1) and twelve-vertex closo-TeB11 Cl11 (2) telluraboranes have been prepared via co-pyrolysis of B2 Cl4 with TeCl4 in vacuo at temperatures between 360 °C and 400 °C. Both compounds are sublimable, off-white solids, and they have been characterized by one- and two-dimensional 11 B NMR and high-resolution mass spectroscopy. Both ab initio/GIAO/NMR and DFT/ZORA/NMR computations support octahedral and icosahedral geometries for 1 and 2, respectively, as expected due to their closo-electron counts. The octahedral structure of 1 has been confirmed by single-crystal X-ray diffraction on an incommensurately modulated crystal. The corresponding bonding properties have been analyzed in terms of the intrinsic bond orbital (IBO) approach. 1 is the first example of a polyhedral telluraborane with a cluster size smaller than 10 vertices.

Anorganisch Chemisches Institut Ruprecht Karls Universität Heidelberg Im Neuenheimer Feld 270 69120 Heidelberg Germany

Institut für Chemie Universität Hohenheim Garbenstrasse 30 70599 Stuttgart Germany

Institute of Inorganic Chemistry of the Czech Academy of Sciences 250 68 Husinec Řež Czech Republic

Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences Flemingovo nám 2 16610 Praha 6 Czech Republic

Present address Zentrum für Nanosystemchemie Universität Würzburg Theodor Boveri Weg 97074 Würzburg Germany

Wilhelm Ostwald Institut für Physikalische und Theoretische Chemie Universität Leipzig Linnéstrasse 2 04103 Leipzig Germany

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Boron-based octahedral dication experimentally detected: DFT surface confirms its availability