Abstract
The title compounds, which are synthesized from be elements, are shown to be isostructural with K8In11 (R3¯c Z=6) and to contain pentacapped trigonal prismatic clusters that have been compressed along the three-fold axes so as to bring the two types of capping atoms within bonding distances. These are arranged in double-ccp layers separated by double alkali--metal layers. Extended Hückel calculations show a substantial energy gap and the end of significant intracluster bonding for the hypoelectronic (by Wade's rules) 18-electron Tl11 7−. Correspondingly, all three compounds are metallic (ρ298 ≈ 400 μΩ · cm) and Pauli-paramagnetic (χM ≈ 4 x 10−4 emu. mol−1, consistent with their formulation as metallic (A +)8Tl11 7− e− phases. Factors thought to be responsible for the cluster distortion, the metallic salt characteristics, and the unusual chemistry of thallium am noted.
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This manuscript is dedicated to Larry Dahl on the occasion of his 65th birthday.
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Dong, ZC., Corbett, J.D. A 8Tl11 (A = K, Rb, or Cs) phases with hypoelectronic Tl11 7− cluster anions: Syntheses, structure, bonding, and properties. J Clust Sci 6, 187–201 (1995). https://doi.org/10.1007/BF01175845
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DOI: https://doi.org/10.1007/BF01175845