TY - JOUR
T1 - Reactions of Beryllium Halides in Liquid Ammonia
T2 - The Tetraammineberyllium Cation [Be(NH3)4]2+, its Hydrolysis Products, and the Action of Be2+as a Fluoride-Ion Acceptor
AU - Kraus, Florian
AU - Baer, Sebastian A.
AU - Buchner, Magnus R.
AU - Karttunen, Antti J.
PY - 2012/2
Y1 - 2012/2
N2 - 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.
AB - 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.
KW - ab initio calculations
KW - beryllium
KW - halides
KW - NMR spectroscopy
KW - X-ray diffraction
KW - LIGAND-EXCHANGE PROCESSES
KW - CRYSTAL-STRUCTURE
KW - X-RAY
KW - COORDINATION CHEMISTRY
KW - NEUTRON-DIFFRACTION
KW - POLY(PYRAZOLYL)BORATE LIGANDS
KW - STRUCTURAL-CHARACTERIZATION
KW - SULPHATE TETRAHYDRATE
KW - SIZE DISCRIMINATION
KW - SYSTEMATIC AFFINITY
U2 - 10.1002/chem.201103012
DO - 10.1002/chem.201103012
M3 - Article
SN - 0947-6539
VL - 18
SP - 2131
EP - 2142
JO - CHEMISTRY: A EUROPEAN JOURNAL
JF - CHEMISTRY: A EUROPEAN JOURNAL
IS - 7
ER -