bis(3-chloropyridyl)dichlorocopper(II) | 21620-64-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: bis(3-chloropyridyl)dichlorocopper(II)
• 英文别名: trans-[CuCl2(3-chloropyridine)2]；trans-[CuCl2(3-Clpy)2]；copper;3-chloropyridine;dichloride
• CAS: 21620-64-4；908605-36-7
• 化学式: C₁₀H₈Cl₄CuN₂
• 分子量: 361.545
• InChiKey: BNHJPMWGFQEODS-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  -2.52
• 重原子数：
  17
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  25.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  盐酸 、 bis(3-chloropyridyl)dichlorocopper(II) 以 neat (no solvent) 为溶剂， 生成 bis(3-chloropyridinium) tetrachlorocuprate(II)
  参考文献：
  名称：

  Reversible Extrusion and Uptake of HCl Molecules by Crystalline Solids Involving Coordination Bond Cleavage and Formation

  摘要：

  Yellow crystalline salts (3-XpyH)2[CuCl4] (3-XpyH = 3-halopyridinium, X = Cl, Br) lose HCl upon exposure to air in an open vessel, yielding quantitatively blue crystalline coordination compounds [CuCl2(3-Xpy)2]. The reaction is prevented if the vessel is sealed, but can be driven forward under such conditions by providing a trapping agent for HCl, such as an aqueous solution of AgNO3. The reaction requires cleavage of Cu-Cl and N-H bonds and formation of Cu-N bonds. The metal coordination geometry also changes from distorted tetrahedral to square planar. Remarkably, the reaction is fully reversible upon exposure of the blue coordination compound to vapor from a concentrated aqueous solution of HCl, and the initial yellow crystalline salt results. The structural changes occurring in these reactions have been followed by X-ray powder diffraction, including Rietveld refinement, of the crystal structures.

  DOI：

  10.1021/ja0625733
• 作为产物：
  描述：

  bis(3-chloropyridinium) tetrachlorocuprate(II) 以 neat (no solvent) 为溶剂， 生成 bis(3-chloropyridyl)dichlorocopper(II)
  参考文献：
  名称：

  Reversible Extrusion and Uptake of HCl Molecules by Crystalline Solids Involving Coordination Bond Cleavage and Formation

  摘要：

  Yellow crystalline salts (3-XpyH)2[CuCl4] (3-XpyH = 3-halopyridinium, X = Cl, Br) lose HCl upon exposure to air in an open vessel, yielding quantitatively blue crystalline coordination compounds [CuCl2(3-Xpy)2]. The reaction is prevented if the vessel is sealed, but can be driven forward under such conditions by providing a trapping agent for HCl, such as an aqueous solution of AgNO3. The reaction requires cleavage of Cu-Cl and N-H bonds and formation of Cu-N bonds. The metal coordination geometry also changes from distorted tetrahedral to square planar. Remarkably, the reaction is fully reversible upon exposure of the blue coordination compound to vapor from a concentrated aqueous solution of HCl, and the initial yellow crystalline salt results. The structural changes occurring in these reactions have been followed by X-ray powder diffraction, including Rietveld refinement, of the crystal structures.

  DOI：

  10.1021/ja0625733

文献信息

• Reversible Gas Uptake by a Nonporous Crystalline Solid Involving Multiple Changes in Covalent Bonding
  作者：Guillermo Mínguez Espallargas、Michael Hippler、Alastair J. Florence、Philippe Fernandes、Jacco van de Streek、Michela Brunelli、William I. F. David、Kenneth Shankland、Lee Brammer

  DOI：10.1021/ja075265t

  日期：2007.12.1

  Hydrogen chloride gas (HCl) is absorbed (and reversibly released) by a nonporous crystalline solid, [CUCl2(3-Clpy)(2)] (3-Clpy = 3-chloropyridine), under ambient conditions leading to conversion from the blue coordination compound to the yellow salt (3-ClpyH)(2)[CUCl4]. These reactions require substantial motions within the crystalline solid including a change in the copper coordination environment from square planar to tetrahedral. This process also involves cleavage of the covalent bond of the gaseous molecules (H-Cl) and of coordination bonds of the molecular solid compound (Cu-N) and formation of N-H and Cu-Cl bonds. These reactions are not a single-crystal-to-single-crystal transformation; thus, the crystal structure determinations have been performed using X-ray powder diffraction. Importantly, we demonstrate. that these reactions proceed in the absence of solvent or water vapor, ruling out the possibility of a water-assisted (microscopic recrystallization) mechanism, which is remarkable given all the structural changes needed for the process to take place. Gas-phase FTIR spectroscopy has permitted us to establish that this process is actually a solid-gas equilibrium, and time-resolved X-ray powder diffraction (both in situ and ex situ) has been used for the study of possible intermediates as well as the kinetics of the reaction.