The Telluraboranes closo‐TeB5Cl5 and closo‐TeB11Cl11 with Exceptionally Long Body Diagonals: Synthetic and Bonding Motifs for Innovative Octahedral and Icosahedral Geometries

Abstract

AbstractSix‐vertex closo‐TeB5Cl5 (1) and twelve‐vertex closo‐TeB11Cl11 (2) telluraboranes have been prepared via co‐pyrolysis of B2Cl4 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 11B 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.