7787-47-5Relevant articles and documents
Crystal structure of [BeCl2(15-Crown-5)]
Neumueller, Bernhard,Dehnicke, Kurt,Puchta, Ralph
, p. 1473 - 1476 (2008)
Single crystals of [BeCl2(15-crown-5)] (1) were obtained from dichloromethane solutions of BeCl2 in the presence of the equivalent amount of 15-crown-5 and characterized by IR spectroscopy and X-ray diffraction. Space group P21/c, Z = 4, lattice dimensions at 100 K: a = 1036.2(1), b = 1071.1(1), c = 1360.1(1) pm, β = 109.86(1)°, R 1 = 0.0225. The structure determination shows no disorder, all hydrogen positions were refined isotropically. The results are in contrast to the previously reported crystal structure determination in the space group P21nb. The beryllium atom of 1 forms a BeO2C2 five-membered heterocycle with terminal chlorine atoms to give a distorted tetrahedral coordination with distances Be-O 166.5(2), 169.9(2) pm, and Be-Cl 195.8(2), 197.8(2) pm. The structural results are in good agreement with DFT calculations on B3LYP/6-311+G** level.
Crystal structure of (Ph4P)2[Be4Cl 4(μ-N3)6]
Neumueller, Bernhard,Dehnicke, Kurt
, p. 1374 - 1376 (2004)
Suitable single crystals for X-ray analysis of the recently published azido beryllate (Ph4P)2[Be4Cl4(μ- N3)6] (1) [1] were obtained by a modified synthetic route, and the crystal structure of 1 was determined. The compound crystallizes isotypically with the corresponding bromo derivative [1] in the space group C2/c with 12 formula units per unit cell. Lattice dimensions at 193 K: a = 4125.5(1) b = 2001.7(1), c = 2050.4(1) pm, β = 101.05 (1)°, R1 = 0.0359. The structure contains adamantanlike dianions [Be4Cl 4(μ-N3)6]2- with a Be 4N6 core forming by the bridging function of the α-nitrogen atoms of the azido groups.
Syntheses, Vibrational Spectra and Crystal Structures of the Chloroberyllates (Ph4P)2[BeCl4] and (Ph 4P)2[Be2Cl6]
Neumüller, Bernhard,Weller, Frank,Dehnicke, Kurt
, p. 2195 - 2199 (2003)
Beryllium dichloride reacts with tetraphenylphosphonium chloride in dichloromethane depending on the molar ratio to give the readily soluble chloroberyllates (Ph4P)2[BeCl4] · 2.5CH2Cl2 (1·2.5CH2Cl2) and (Ph4P)2[Be2Cl6]·2CH 2Cl2 (2·2CH2Cl2), respectively. Both compounds are characterized by crystal structure determinations. 1·2.5CH2Cl2: Space group P1?, Z = 2, lattice dimensions at 193 K: a = 1185.7(1), b = 1244.5(1), c = 1939.3(2) pm, α = 77.62(1)°, β = 74.13(1)°, γ = 68.17(1)°, R1 = 0.0416. The [BeCl4]2- ion forms tetrahedra without special site symmetry. 2·2CH2Cl 2: Space group P1?, Z = 1, lattice dimensions at 193 K: a = 985.3(1), b = 1107.6(1), c = 1344.7(1) pm, α = 65.45(1)°, β = 79.12(1)°, γ = 78.49(1)°, R1 = 0.0361. The [Be 2Cl6]2- ion forms chloro-bridged double tetrahedra with site symmetry 1? (Ci). Both compounds lose the included dichloromethane in vacuo. The vibrational spectra (IR, Raman) of 1 and 2 are reported.
[Be(OH2)4]Cl2 - Preparation, IR spectrum, and crystal structure
Massa, Werner,Dehnicke, Kurt
, p. 1366 - 1370 (2007)
Single crystals of [Be(OH2)4]Cl2 were prepared by the reaction of thionyl chloride at 20 °C with samples which result from evaporated, HCl containing, aqueous solutions of BeCl2. With excess of boiling thionyl chloride BeCl2 is formed. [Be(OH 2)4]Cl2 is characterized by IR spectroscopy and by X-ray crystal structure determination: Space group P21/c, Z = 4, lattice dimensions at 193 K: a = 653.53(5), b = 1298.15(14), c = 789.52(6) pm, β= 103.005(9)°, R1 = 0.027. The structure consists of slightly distorted tetrahedral [Be(OH2)2]2+ ions, which are connected with the chloride ions via nearly linear O-H...Cl hydrogen bonds to give a 3D network.
A facile synthesis for BeCl2, BeBr2 and BeI2
Müller, Matthias,Pielnhofer, Florian,Buchner, Magnus R.
, p. 12506 - 12510 (2018/09/27)
Here we present a facile synthesis for anhydrous BeCl2, BeBr2 and BeI2 from the elements under mild conditions. While this method delivers pure BeI2 directly, BeCl2 and BeBr2 were further purified by vacuum sublimation. Complete sets of solid state IR and Raman spectroscopic and X-ray powder diffraction data of these beryllium halides were collected including the previously missing IR and Raman spectra of BeBr2 and BeI2. All halides were additionally investigated by quantum chemical calculations. This allowed an assignment of the IR and Raman modes, which had never been done before on any beryllium halide and allowed interpretation of the experimental data as well as the differentiation of polymorphs.
Infrared Spectroscopic and Electronic Structure Investigations of Beryllium Halide Molecules, Cations, and Anions in Noble Gas Matrices
Yu, Wenjie,Andrews, Lester,Wang, Xuefeng
, p. 8843 - 8855 (2017/12/05)
Laser-ablated Be atoms, cations, and electrons were reacted with F2, ClF, Cl2, NF3, CCl4, CF2Cl2, HCl, DCl, and SiCl4 diluted in noble gases. The major products were the dihalides BeF2, BeClF, BeCl2, and the hydride chloride HBeCl, whose identities were confirmed by comparison with previous evaporative work, deuterium substitution, and vibrational frequency calculations. The matrix-isolated fundamental frequency of the BeF molecule is higher, and the frequency of BeCl is lower, than that determined for the gas-phase molecules. The BeF+ and BeCl+ cations formed strong dipole-induced dipole complexes in solid Ne, Ar, Kr, and Xe with stepwise increase in computed noble gas dissociation energies. Going down the family NgBeF+ and NgBeCl+ series (Ng = Ne, Ar, Kr, Xe) the Mulliken charges q(Be) decrease, while q(Ng) increases, and the dipole moments decrease, which suggests covalent bonding in the xenon species. We find that the largest intramatrix shift is Ne to Ar which follows the largest factor increase for the Ng atomic polarizabilities. Extra electrons produce Cl-, which reacts with HCl to form the stable HCl2- anion and possibly with BeCl2 to give BeCl3-. A weak band observed in neon experiments with F2 is probably due to BeF3-.
About the reaction of BeCl2 with the carbodiphosphorane addition compound O2C←C(PPh3)2 and its hydrolysis product Ph3PCHP(O)Ph2
Petz, Wolfgang,Dehnicke, Kurt,Neumueller, Bernhard
, p. 1761 - 1768 (2012/01/04)
Abstract. Reaction of BeCl2 and (PPh4)[Be 2Cl6] with Ph3PCHP(O)Ph2 (2) and of BeCl2 with O2C←C(PPh3)2 (3) were studied under various conditions. Whereas the addition compound of 2 with BeCl2 could only traced by 31P NMR spectroscopy the molecular structure of the O-addition compound [Ph3PCH 2P(OBeCl3)Ph2]·0.75CH2Cl 2 (5) from 2 and (PPh4)[Be2Cl6] could be performed. From 3 and BeCl2 in dichloromethane crystals of (H2C{PPh3}2)[BeCl4] (6) and (H 2C{PPh3}2)Cl2·CH 2Cl2 (7) separated. The cluster [Be6(OH) 6Cl5(O2C2{PPh3} 2)3]Cl(8) formed upon unintentionally admitting some humidity to the initial reaction mixture. In 8 each of the bidentate ligands 3 bridges two different beryllium atoms via the oxygen atoms. All compounds are characterized by X-ray diffraction analyses. Copyright
Trichloroberyllate complexes of dimethyl cyanamide, morpholine, and 4,4′-bipyridine
Neumueller, Bernhard,Dehnicke, Kurt
, p. 1206 - 1212 (2008/10/09)
The trichloroberyllate complexes (Ph4P)[BeCl 3(NCNMe2)] (1), (Ph4P)[BeCl 3{HN(CH2)4O}] (2), and (Ph4P) 2[(BeCl3)2(4,4′-bipy)] (3) were prepared by reactions of (Ph4P)2[Be2Cl6] with dimethyl cyanamide, trimethylsilylmorpholinate, and 4,4′-bipyridine, respectively, in dichloromethane solutions. 1-3 were characterized by X-ray crystallography and by IR-spectroscopy. 1·CH2Cl2: Space group P1, Z = 1, lattice dimensions at 173 K: a = 714.2(1), b = 919.5(2), c = 1233.4(2) pm, α = 94.97(1)°, β = 90.86(1)°, γ = 111.90(1)°, R1 = 0.0310. In the complex anion [BeCl 3(NCNMe2)]- the dimethyl cyanamide ligand is coordinated via a linear Be-N≡C-NMe2 arrangement, the CH 2Cl2 molecules forming linear chains by hydrogen bridges ...HCH...Cl... with the chlorine atoms of the {BeCl 3-} groups. 2: Space group P1, Z = 2, lattice dimensions at 173 K: a = 1050.9(1), b = 1099.7(1), c = 1308.3(2) pm, α = 87.57(1)°, β = 70.97(1)°, γ = 74.58(1)°, R1 = 0.0397. The complex anions are dimerized by centrosymmetric puckered eight-membered [Be-N-H...Cl]2 rings. 3·2CH 2Cl2: Space group P1, Z = 2, lattice dimensions at 173 K: a = 1095.4(1), b = 1559.6(2), c = 1869.8(3) pm, α = 79.12(1)°, β = 73.83(1)°, γ = 78.76(1)°, R1 = 0.0548. The complex contains dianions [Cl3Be(μ-bipy)BeCl3]2- with Be-N distances of 177.0(6) and 178.5(6) pm. Both {BeCl3) - groups form C-H...Cl hydrogen bridges with the dichloromethane molecules.
Synthesis, experimental/theoretical characterization, and thermolysis chemistry of CpBe(SiMe3), a molecule containing an unprecedented beryllium-silicon bond
Saulys, Dovas A.,Powell, Douglas R.
, p. 407 - 413 (2008/10/08)
The synthesis, characterization, and thermal decomposition of CpBe(SiMe3) are presented as part of an exploratory investigation designed to obtain more effective chemical vapor deposition precursors of metallic beryllium. The title compound provides the first example of a direct bond between beryllium and a non-carbenoid group 14 element. The base-free reaction of LiSiMe3 with CpBeCl in pentane affords the air-sensitive, volatile solid CpBe(SiMe3) (ca. 70% yield based on CpBeCl), which was characterized by single-crystal CCD X-ray diffraction, multinuclear NMR, and mass spectrometric studies, and theoretically by DFT/NBO analysis. The solid-state molecular geometry of CpBe(SiMe3) ideally conforms to C3v symmetry (under assumed cylindrical symmetry for the C5H5 ring); the Be-Si bond length of 2.185(2) A is markedly longer than the sum of covalent radii (2.01 A). The DFT-optimized molecular geometry closely conforms to that determined crystallographically. Total fragment charges (based upon atomic charge NBO calculations) of -0.79 e for C5H5, +1.26 e for Be, +0.81 e for Si, and -1.28 e for the three Me groups constitute a polarity pattern consistent with the Be-Cp bonding interaction being mainly ionic and with the Be-Si bonding pair being polarized toward the more electronegative SiMe3 fragment. Beryllium-9 and 29Si NMR spectra exhibit a large J(Be-Si) coupling constant of 51 Hz; the 9Be chemical shift of δ -27.70 ppm, the highest field value recorded to date, is in accordance with the calculated bond-polarity pattern, as well as a bond to Si. Mass spectra (EI) exhibited peaks for the molecular ion and its isotopomers. Thermal decomposition of CpBe(SiMe3) gives rise to trimethylsilane, CpBeMe, and CpBe(SiMe2SiMe3) as the major products, as determined by multinuclear NMR. The latter species is likewise formed by the reaction of CpBeCl with LiSiMe2SiMe3.
Crystal Structure of Beryllium Nitrate Complexes (NO)2[Be(NO3)4] and Be4O(NO3)6
Troyanov,Tikhomirov,Znamenkov,Morozov
, p. 1791 - 1798 (2008/10/08)
Dinitrosonium tetranitratoberyllate (NO)2[Be(NO3)4] (I) was prepared by the reaction of BeCl2 with liquid N2O4 in the presence of ethyl acetate. The crystal structure of I is orthorhombic: a = 13.471(4) ?, b = 23.910(6) ?, c = 6.229(2) ?, Z= 8, space group Fdd2, R1, = 0.0412. The structure is built from nitrosonium cations (N-O 0.916(9) ?) and [Be(NO3)4]2- anions with tetrahedral coordination of Be (the Be-O distances are 1.627-1.641(9) ?) and monodentate nitrato groups. The thermal decomposition of I yields trigonal modification of beryllium oxonitrate, Be4O(NO3)6 (II): a = 13.638(3) ?, c = 6.475(2) ?, Z = 3, space group P3, R1 = 0.0585. The structure of II is built of tetranuclear Be4O(NO3)6 molecules with the tetracoordinated central O atom (Be-O 1.59-1.64 ?), forming the OBe4 tetrahedron, and six bidentate NO3 groups coordinated to each of the Be?Be edges with the Be-O distances of 1.60-1.72 ?. It seems that O is a high-temperature modification of beryllium oxonitrate.
