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Reactions of Beryllium Halides in Liquid Ammonia: The Tetraammineberyllium Cation [Be(NH 3 ) 4 ] 2+ , its Hydrolysis Products, and the Action of Be 2+ as a Fluoride‐Ion Acceptor
Author(s) -
Kraus Florian,
Baer Sebastian A.,
Buchner Magnus R.,
Karttunen Antti J.
Publication year - 2012
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201103012
Subject(s) - chemistry , ammonia , halide , inorganic chemistry , nuclear magnetic resonance spectroscopy , molecule , medicinal chemistry , hydrolysis , raman spectroscopy , ion , fluoride , infrared spectroscopy , crystallography , stereochemistry , organic chemistry , physics , optics
The first structural characterization of the text‐book tetraammineberyllium(II) cation [Be(NH 3 ) 4 ] 2+ , obtained in the compounds [Be(NH 3 ) 4 ] 2 Cl 4 ⋅ 17NH 3 and [Be(NH 3 ) 4 ]Cl 2 , is reported. Through NMR spectroscopic and quantum chemical studies, its hydrolysis products in liquid ammonia were identified. These are the dinuclear [Be 2 (μ‐OH)(NH 3 ) 6 ] 3+ and the cyclic [Be 2 (μ‐OH) 2 (NH 3 ) 4 ] 2+ and [Be 3 (μ‐OH) 3 (NH 3 ) 6 ] 3+ cations. The latter species was isolated as the compound [Be 3 (μ‐OH) 3 (NH 3 ) 6 ]Cl 3 ⋅ 7NH 3 . NMR analysis of solutions of BeF 2 in liquid ammonia showed that the [BeF 2 (NH 3 ) 2 ] molecule was the only dissolved species. It acts as a strong fluoride‐ion acceptor and forms the [BeF 3 (NH 3 )] − anion in the compound [N 2 H 7 ][BeF 3 (NH 3 )]. The compounds presented herein were characterized by single‐crystal X‐ray structure analysis, 9 Be, 17 O, and 19 F 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.