bis(5,6-dihydro-5,6-epoxy-1,10-phenanthroline)copper(I) perchlorate | 1268524-76-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: bis(5,6-dihydro-5,6-epoxy-1,10-phenanthroline)copper(I) perchlorate
• CAS: 1268524-76-0
• 化学式: C₂₄H₁₆CuN₄O₂*ClO₄
• 分子量: 555.413
• InChiKey: HXNSMPPGICDOSC-AVGPOFISSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为产物：
  描述：

  tetrakis(acetonitrile)copper(I) perchlorate 、 5,6-环氧-5,6-二氢-[1,10]菲咯啉 以 甲醇 为溶剂， 以55%的产率得到bis(5,6-dihydro-5,6-epoxy-1,10-phenanthroline)copper(I) perchlorate
  参考文献：
  名称：

  Homoleptic copper(II) and copper(I) complexes of 5,6-dihydro-5,6-epoxy-1,10-phenanthroline. Six-coordinate copper(I) in solution

  摘要：

  Reaction of 5,6-dihydro-5,6-epoxy-1,10-phenanthroline (L) with Cu(ClO4)(2)center dot 6H(2)O in methanol in 3:1 M ratio at room temperature yields light green [CuL3](ClO4)(2)center dot H2O (1). The X-ray crystal structure of the hemi acetonitrile solvate [CuL3](ClO4)(2)center dot 0.5CH(3)CN has been determined which shows Jahn-Teller distortion in the CuN6 core present in the cation [CuL3](2+). Complex 1 gives an axial EPR spectrum in acetonitrile-toluene glass with g(parallel to) = 2.262 (A(parallel to) = 169 x 10 (4) cm (1)) and g(perpendicular to) = 2.069. The Cu(II/I) potential in 1 in CH2Cl2 at a glassy carbon electrode is 0.32 V versus NHE. This potential does not change with the addition of extra L in the medium implicating generation of a six-coordinate copper(I) species [CuL3](+) in solution. B3LYP/LanL2DZ calculations show that the six Cu-N bond distances in [CuL3](+) are 2.33, 2.25, 2.32, 2.25, 2.28 and 2.25 angstrom while the ideal Cu(I)-N bond length in a symmetric Cu(I)N-6 moiety is estimated as 2.25 angstrom. Reaction of L with Cu(CH3CN)(4)ClO4 in dehydrated methanol at room temperature even in 4:1 M proportion yields [CuL2]ClO4 (2). Its H-1 NMR spectrum indicates that the metal in [CuL2](+) is tetrahedral. The Cu(II/I) potential in 2 is found to be 0.68 V versus NHE in CH2Cl2 at a glassy carbon electrode. In presence of excess L, 2 yields the cyclic voltammogram of 1. From H-1 NMR titration, the free energy of binding of L to [CuL2](+) to produce [CuL3](+) in CD2Cl2 at 298 K is estimated as -11.7 (+/-0.2) kJ mol (1). (C) 2010 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2010.10.026