lithium amide-d2 | 12159-23-8

• 英文名称: lithium amide-d2
• CAS: 12159-23-8
• 化学式: H₂LiN
• 分子量: 24.9477
• InChiKey: AFRJJFRNGGLMDW-ZSJDYOACSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.97
• 重原子数：
  2.0
• 可旋转键数：
  0.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  26.02
• 氢给体数：
  1.0
• 氢受体数：
  1.0

反应信息

• 作为产物：
  描述：

  lithium 、 氨-d3 以 neat (no solvent, gas phase) 为溶剂， 生成 lithium amide-d2
  参考文献：
  名称：

  First Synthesis and Structural Determination of a Monomeric, Unsolvated Lithium Amide, LiNH₂

  摘要：

  Alkali metal amides typically aggregate in solution and the solid phase, and even in the gas phase. In addition, even in the few known monomeric structures, the coordination number of the alkali metal is raised by binding of Lewis-basic solvent molecules, with concomitant changes in structure. In contrast, the simplest lithium amide LiNH2 has never been made in a monomeric form, even though its structure has been theoretically predicted several times. Here, the first experimental structural data for a monomeric, unsolvated lithium amide are determined using a combination of gas-phase synthesis and millimeter/submillimeter-wave spectroscopy. All data point to a planar structure for LiNH2. The r(o) structure of LiNH2 has a Li-N distance of 1.736(3) Angstrom, an N-H distance of 1.022(3) Angstrom, and a H-N-H angle of 106.9(1)degrees. These results are compared with theoretical predictions for LiNH2, and experimental data for oligomeric, solid-phase samples, which could not resolve the question of whether LiNH2 is planar or not. In addition, comparisons are made with revised gas-phase and solid-phase data and calculated structures of NaNH2.

  DOI：

  10.1021/ja003422h

文献信息

• Structure of Ternary Imide Li₂Ca(NH)₂ and Hydrogen Storage Mechanisms in Amide−Hydride System
  作者：Hui Wu

  DOI：10.1021/ja800300e

  日期：2008.5.1

  The crystal structure of the ternary imide Li2Ca(NH)(2) has been determined using neutron powder diffraction data on a deuterated sample. The structure consists of infinite layers of edge-shared Ca[NH](6) octahedra, which are separated by Li cations. The mobile Li+ ions in such two-dimensional channels defined by Ca[NH](6) octahedra layers are shown to have a great impact on the hydrogenation properties of the imide. Through detailed structural analysis on the products at various stages of desorption and absorption of the amide-hydride mixture, we proposed a dehydrogenation mechanism involving the mobile small ions in both amide and hydride and a hydrogen storage mechanism for the ternary imide.
• The crystal structure of LiND2 and Mg(ND2)2
  作者：M.H. Sørby、Y. Nakamura、H.W. Brinks、T. Ichikawa、S. Hino、H. Fujii、B.C. Hauback

  DOI：10.1016/j.jallcom.2006.03.037

  日期：2007.1

  The crystal structures of LiND2 and Mg(ND2)(2) have been investigated by high-resolution powder neutron and synchrotron X-ray diffraction. LiND2 takes a tetragonal crystal structure (space group I4, a = 5.03164(8) angstrom, c = 10.2560(2) angstrom). The Li+ ions are tetrahedrally coordinated by four amide (ND2-) ions with Li-N separations ranging between 2.065(3) and 2.210(3) angstrom. The two N-D distances are similar (0.967(5) and 0.978(6) angstrom) and the D-N-D angle is 104.0(7)degrees, which are very close to the isoelectronic water molecule. The neutron diffraction data for Mg(ND2)2 are fitted well with a tetragonal unit cell (space group I4(1)/acd, a = 10.3758(6) angstrom, c = 20.062(1) angstrom), although the powder synchrotron X-ray diffraction data indicate that the symmetry may be lower. The cation is again tetrahedrally coordinated by four amide ions. The Mg-N distances are between 2.00(1) and 2.17(1) angstrom. The N-D separations and D-N-D angles in the three different amide ions are in the range of 0.95(1)-1.07(1) angstrom and 101(1)-107(2)degrees, respectively. The Mg(ND2)(2) structure can alternatively be described as a pseudo-fec lattice of Mg-4 tetrahedra with amide anions in all tetrahedral interstices and six amide ions distributed in the periphery of each octahedral interstices, giving a slightly distorted octahedral arrangement of amide units around each Mg-4 tetrahedron. (c) 2006 Elsevier B.V. All rights reserved.
• Infrared and Raman studies on the internal modes of lithium amide
  作者：J.-P.O. Bohger、R.R. Eßmann、H. Jacobs

  DOI：10.1016/0022-2860(95)08654-e

  日期：1995.3

  Infrared and Raman spectra of LiNH2 and LiND2 as well as of isotopically diluted samples, LiN(H,D)(2), are reported and discussed with respect to structural and bonding features of the amide ion in condensed phases in comparison to crystalline hydrates and hydroxides. Due to the high charge density of the Li+-ion the NH-stretching modes are shifted to higher energy (Delta<(nu)over tilde>approximate to 130cm(-1)) compared to the free ion. They are split into two components in the uncoupled NHD--ions contained in partially diluted samples, caused by two crystallographic nonequivalent hydrogen atoms. Despite of the high charge density of the Li+-ion the proton donor strength of the amide is not enlarged in a way that hydrogen bonds could be observed - neither spectroscopically (temperature shift of NH-stretching modes) nor crystallographically.
• Hydrogen Desorption Mechanism in a Li−N−H System by Means of the Isotopic Exchange Technique
  作者：Shigehito Isobe、Takayuki Ichikawa、Satoshi Hino、Hironobu Fujii

  DOI：10.1021/jp051889e

  日期：2005.8.1

  The hydrogen desorption mechanism in the reaction from LiH + LiNH2 to Li2NH + H-2 was examined by thermal desorption mass spectrometry, thermogravimetric analysis, and Fourier transform IR analyses for the products replaced by LiD or LiND2 for LiH or LiNH2, respectively. The results obtained indicate that the hydrogen desorption reaction proceeds through the following two-step elementary reactions mediated by ammonia: 2LiNH(2) -> Li2NH + NH3 and LiH + NH3 - LiNH2 + H-2, where hydrogen molecules are randomly formed from four equivalent hydrogen atoms in a hypothetical LiNH4 produced by the reaction between LiH and NH3 according to the laws of probability.