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1.
Masataka Hiraide Kennich Ishikawa Zuo Sheng Chen Hiroshi Kawaguchi 《Mikrochimica acta》1994,117(1-2):7-13
Coprecipitation first with magnesium hydroxide, next with tin(IV) hydroxide is developed for the determination of traces of beryllium in sea-water. To a 200-ml sample is added a sodium hydroxide solution to form magnesium hydroxide at pH 11.5, on which beryllium is quantitatively coprecipitated. The precipitate is separated by centrifugation and dissolved in 2 ml of 12 mol/l hydrochloric acid. The resulting solution (ca. 10 ml) is mixed with 2 mg of tin (IV) carrier and the pH is adjusted to 5.0 to collect the beryllium on tin (IV) hydroxide, leaving magnesium ions in the solution. The tin (IV) hydroxide is centrifuged, dissolved in 0.1 ml of 5 mol/l hydrobromic acid, and then diluted to 1 ml with water. Magnesium is so added as to be 500 g/ml for increasing the sensitivity about four times, and the beryllium in the solution is determined by graphite furnace atomic absorption spectrometry. The experiments with synthetic seawater samples showed that pg — g amounts of beryllium can be coprecipitated on the metal hydroxides and beryllium at the low ng/1 level can be determined with reasonable precision (RSD < 10%). The detection limit of the proposed method is 0.5 ng/l of beryllium in seawater. 相似文献
2.
del Mar Conejo M Fernández R del Río D Carmona E Monge A Ruiz C Márquez AM Sanz JF 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(18):4452-4461
The beryllocenes [Be(C(5)Me(4)H)(2)] (1), [Be(C(5)Me(5))(2)] (2), and [Be(C(5)Me(5))(C(5)Me(4)H)] (3) have been prepared from BeCl(2) and the appropriate KCp' reagent in toluene/diethyl ether solvent mixtures. The synthesis of 1 is facile (20 degrees C, overnight), but generation of decamethylberyllocene 2 demands high temperatures (ca. 115 degrees C) and extended reaction times (3-4 days). The mixed-ring beryllocene 3 is obtained when the known [(eta(5)-C(5)Me(5))BeCl] is allowed to react with K[C(5)Me(4)H], once more under somewhat forcing conditions (115 degrees C, 36 h). The structures of the three metallocenes have been determined by low-temperature X-ray studies. Both 1 and 3 present eta5/eta1 geometries of the slip-sandwich type, whereas 2 exhibits an almost regular, ferrocene-like, sandwich structure. In the mixed-ring compound 3, C(5)Me(5) is centrally bound to beryllium and the eta(1)-C(5)Me(4)H ring bonds to the metal through the unique CH carbon atom. This is also the binding mode of the eta(1)-ring of 1. To analyze the nature of the bonding in these molecules, theoretical calculations at different levels of theory have been performed on compounds 2 and 3, and a comparison with the bonding in [Be(C(5)H(5))(2)] has been made. As for the latter molecule, energy differences between the eta5/eta5 and the eta5/eta1 structures of 2 are very small, being of the order of a few kcal mol(-1). Constrained space orbital variations (CSOV) calculations show that the covalent character in the bonding is larger for [Be(C(5)Me(5))(2)] than for [Be(C(5)H(5))(2)] due to larger charge delocalization and to increased polarizability of the C(5)Me(5) fragment. 相似文献
3.
Matthias Müller Dr. Magnus R. Buchner 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(44):9915-9922
The first synthesis of BePh2 was accomplished almost a century ago. However, its structure has remained unknown so far, while the corresponding aryls of the elements adjacent to beryllium in the periodic table are well investigated. Herein, we present an improved synthesis for diphenylberyllium and show by X-ray diffraction that it forms a trinuclear complex in the solid state. NMR spectroscopy revealed that this structure is also retained in solution but exhibits dynamic behavior. Its stability against heat and coordinating solvents is discussed and the possible obstacles to the synthesis of BePh2 from BeCl2 are examined. In the process of this study two ether adducts, BePh2⋅Et2O and Be2Ph4⋅Et2O, have been characterized as well as the previously unknown triphenylberyllate anion. From the latter several single-crystal structures were obtained under various conditions, in which [BePh3]− is either isolated or acts as a ligand for Li+. Furthermore, the crown ether induced selfionization of BePh2 is described and the resulting [(12-crown-4)BePh]+ cation was isolated, which shows an unusual 4+1 coordination around the Be atom. 相似文献
4.
An analysis of the effects induced by F, Cl, and Br-substituents at the α-position of both, the hydroxyl or the amino group for a series of amino-alcohols, HOCH2(CH2)nCH2NH2 (n = 0–5) on the strength and characteristics of their OH···N or NH···O intramolecular hydrogen bonds (IMHBs) was carried out through the use of high-level G4 ab initio calculations. For the parent unsubstituted amino-alcohols, it is found that the strength of the OH···N IMHB goes through a maximum for n = 2, as revealed by the use of appropriate isodesmic reactions, natural bond orbital (NBO) analysis and atoms in molecules (AIM), and non-covalent interaction (NCI) procedures. The corresponding infrared (IR) spectra also reflect the same trends. When the α-position to the hydroxyl group is substituted by halogen atoms, the OH···N IMHB significantly reinforces following the trend H < F < Cl < Br. Conversely, when the substitution takes place at the α-position with respect to the amino group, the result is a weakening of the OH···N IMHB. A totally different scenario is found when the amino-alcohols HOCH2(CH2)nCH2NH2 (n = 0–3) interact with BeF2. Although the presence of the beryllium derivative dramatically increases the strength of the IMHBs, the possibility for the beryllium atom to interact simultaneously with the O and the N atoms of the amino-alcohol leads to the global minimum of the potential energy surface, with the result that the IMHBs are replaced by two beryllium bonds. 相似文献
5.
Tsai I-Ting M. Merced Montero-Campillo Ibon Alkorta Jos Elguero Manuel Yez 《Molecules (Basel, Switzerland)》2021,26(11)
Intramolecular interactions are shown to be key for favoring a given structure in systems with a variety of conformers. In ortho-substituted benzene derivatives including a beryllium moiety, beryllium bonds provide very large stabilizations with respect to non-bound conformers and enthalpy differences above one hundred kJ·mol−1 are found in the most favorable cases, especially if the newly formed rings are five or six-membered heterocycles. These values are in general significantly larger than hydrogen bonds in 1,2-dihidroxybenzene. Conformers stabilized by a beryllium bond exhibit the typical features of this non-covalent interaction, such as the presence of a bond critical point according to the topology of the electron density, positive Laplacian values, significant geometrical distortions and strong interaction energies between the donor and acceptor quantified by using the Natural Bond Orbital approach. An isodesmic reaction scheme is used as a tool to measure the strength of the beryllium bond in these systems in terms of isodesmic energies (analogous to binding energies), interaction energies and deformation energies. This approach shows that a huge amount of energy is spent on deforming the donor–acceptor pairs to form the new rings. 相似文献
6.
Beryllium fluorides are widely used in protein phosphorylation studies to get stable transition state analogs or near attack conformers, which has attracted much attention. BeF3? is one of the optimal phosphoryl (PO3?) analogs for its identical geometry and charge, and Mg2+ naturally participates in the phosphoryl binding in biological systems. In solutions, BeF3? coexists with other beryllium fluorides (BeF42?, BeF2 and BeF+) and magnesium fluorides, and there are equilibriums between these species. In this article, 19F NMR spectroscopy was applied to the investigation of the impact of magnesium(II) on beryllium fluorides. It has been found that when Mg2+ was introduced into the solutions, the chemical shifts, the intensities and the line widths of 19F signals of various beryllium fluoride complexes were changed. After ionic strength correction, these effects were remarkable only for BeF42? and BeF3?, especially BeF42?, when the concentration of the fluoride ion is relatively low. Mechanism of the effects is proposed which involves ion pair formation between Mg2+ and beryllium fluorides. 相似文献
7.
8.
A new set of trial functions for 1s^22sns configurations in a beryllium atom is suggested. A Mathematica program based on the variational method is developed to calculate the wavefunctions and energies of 1s^22sns (n = 3 - 6) configurations in a beryllium atom. Non-relativistic energy, polarization correction and relativistic correction which include mass correction, one- and two-body Darwin corrections, spin-spin contact interaction and orbit-orbit interaction, are calculated respectively. The results are in good agreement with experimental data. 相似文献
9.
简述了BeH2材料的制备方法、结构形式和物理化学性质,并分析了其在惯性约束聚变(ICF)中的应用。BeH2材料主要由二叔丁基铍热解法和元素化学气相沉积法制备,其纯度(质量分数)高达99%。非晶BeH2材料的结构是一种共用氢原子作为顶点的BeH4四面体网络结构。非晶BeH2材料不仅具有铍的优点,还具有聚合物的优点,作为ICF靶可以降低瑞利-泰勒不稳定性,而且掺入高Z元素后还可以降低D-T燃料的预热。非晶BeH2材料作为烧蚀层,掺入高Z元素后可以提高激光-X光的转换效率。 相似文献
10.