Mercury(II) complexes of the carba- closo -dodecaboranyl ligands [ closo -1-CB X ] (X = H, F, Cl, Br, I)
Organometallics, ISSN: 0276-7333, Vol: 31, Issue: 4, Page: 1566-1577
2012
- 20Citations
- 4Captures
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Article Description
Salts of the mercury(II) complexes [Hg(closo-1-CB X ) ] (X = H (1), Cl (3), Br (4)) and [PhHg(closo-1-CB X )] (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 Cs 1•2Et O, Cs 3•MeCN, Cs 4•4Me CO, Cs9, and [Et N]6•0. 5Me CO 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-CB F ) ] (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-dodecaboranyl ligands [closo-1-CB X ] (X = Cl, Br). The dianionic complex [Hg(closo-1-CB I ) ] (5) with the bulkiest carba-closo-dodecaboranyl ligand was generated via collision-induced dissociation and characterized by (-)-ESI mass spectrometry. The fragmentation pathways of the anionic complexes [Hg(closo-1-CB X ) ] (X = H, F, Cl, Br, I (1-5)) and [PhHg(closo-1-CB X )] (X = H, F, Cl, Br, I (6-10)) were studied by (-)-ESI mass spectrometry. © 2011 American Chemical Society.
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