Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 18, Issue 7, Pages 2131-2142Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201103012
Keywords
ab initio calculations; beryllium; halides; NMR spectroscopy; X-ray diffraction
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Funding
- Academy of Finland [138560/2010]
- Fonds der Chemischen Industrie
- Deutsche Forschungsgemeinschaft
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The first structural characterization of the text-book tetraammineberyllium(II) cation [Be(NH3)4]2+, obtained in the compounds [Be(NH3)4]2Cl4.17NH3 and [Be(NH3)4]Cl2, is reported. Through NMR spectroscopic and quantum chemical studies, its hydrolysis products in liquid ammonia were identified. These are the dinuclear [Be2(mu-OH)(NH3)6]3+ and the cyclic [Be2(mu-OH)2(NH3)4]2+ and [Be3(mu-OH)3(NH3)6]3+ cations. The latter species was isolated as the compound [Be3(mu-OH)3(NH3)6]Cl3.7NH3. NMR analysis of solutions of BeF2 in liquid ammonia showed that the [BeF2(NH3)2] molecule was the only dissolved species. It acts as a strong fluoride-ion acceptor and forms the [BeF3(NH3)]- anion in the compound [N2H7][BeF3(NH3)]. The compounds presented herein were characterized by single-crystal X-ray structure analysis, 9Be, 17O, and 19F NMR, IR, and Raman spectroscopy, deuteration studies, and quantum chemical calculations. The extension of beryllium chemistry to the ammine system shows similarities but also decisive differences to the aquo system.
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