Alexander Himmelspach, J. Sprenger, J. Warneke
Feb 27, 2012
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Organometallics
Abstract
Salts of the mercury(II) complexes [Hg(closo-1-CB11X11)2]2– (X = H (1), Cl (3), Br (4)) and [PhHg(closo-1-CB11X11)]− (X = H (6), Cl (8), Br (9), I (10)) were synthesized and characterized by multi-NMR spectroscopy, mass spectrometry, elemental analysis, and differential scanning calorimetry. Single crystals of Cs21·2Et2O, Cs23·MeCN, Cs24·4Me2CO, Cs9, and [Et4N]6·0.5Me2CO were studied by X-ray diffraction, and the interpretation of the bond properties is supported by theoretical data. In contrast to the mercury atom of the previously published [Hg(closo-1-CB11F11)2]2– (2), which coordinates either acetonitrile or water, the metal atom of the related dianionic complexes 1, 3, and 4 does not reveal any further coordination. According to results derived from DFT and ab initio calculations, this different behavior is reasoned in the case of 1 by a reduced Lewis acidity at mercury and in the case of 3 and 4 by the increased shielding of the central mercury atom as a result of the bulky halogenated carba-closo-d...