N,N'-bis{(2-(phenylmethylthio)phenyl)methylene}ethane-1,2-diaminecopper(I) perchlorate | 143672-47-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: N,N'-bis{(2-(phenylmethylthio)phenyl)methylene}ethane-1,2-diaminecopper(I) perchlorate
• CAS: 143672-47-3
• 化学式: C₃₀H₂₈CuN₂S₂*ClO₄
• 分子量: 643.694
• InChiKey: LYPBTKKTYIMKOV-SMCCFYDVSA-M

计算性质

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

反应信息

• 作为反应物：
  描述：

  N,N'-bis{(2-(phenylmethylthio)phenyl)methylene}ethane-1,2-diaminecopper(I) perchlorate 在 air 作用下， 以 乙醇 为溶剂， 生成 aqua{(N,N'-bis({2-(phenylmethylthio)phenyl}methylene)ethane-1,2-diamine-S,S',N,N')}copper(II) perchlorate
  参考文献：
  名称：

  Crystal structures, dynamic behaviour and electrochemical properties of the copper-(I) and -(II) complexes of a new N2S2 ligand

  摘要：

  The complexing properties of the new quadridentate N2S2 ligand N,N'-bis{[2-(phenylmethylthio)phenyl]methylene} ethane-1,2-diamine, L, with Cu(I) and Cu(II) have been investigated. The perchlorate salt of [CuL]+ occurs as orange crystals in which mirror image forms, [(+/-)-(R*,R*,S*)], of the highly distorted tetrahedral cation coexist. The CuN2-CuS2 dihedral angle = 60.0(1)-degrees, bond lengths and angles are Cu-S 2.285(1) and 2.258(1) angstrom, Cu-N 2.029(3) and 2.069(3) angstrom, N-Cu-N 82.7(1)-degrees, S-Cu-S 123.56(4)-degrees. In nitromethane solution, however, variable-temperature C-13 NMR spectroscopy indicates that [CuL]+ exists predominantly as an equilibrium mixture of the two other diastereomers, [(+/-)-(R*,R*,R*)] and [(+/-)R*, S*,S*)] for which the interconversion barrier corresponds to DELTA-G280 = 59.8 +/- 0.6 kJ mol 1. Exposure of an ethanolic solution of [CuL]ClO4 to the atmosphere leads to slow deposition of brown crystals of [CuL(H2O)][ClO4]2. Crystal structure determination revealed the Cu(II) cation to be square-pyramidal with the water molecule occupying the apical position: Cu-S 2.323(6) and 2.318(5) angstrom; Cu-N 1.94(1) and 2.00(2) angstrom; Cu-O (H2O) 2.29(1) angstrom. The crystals are achiral and racemic, arising through coexistence of the [(+/-)-(R*,R*)] enantiomeric forms of the complex. Cyclic voltammetry indicates a quasi-reversible system for which E1/2 = 0.28 V vs. saturated calomel electrode.

  DOI：

  10.1039/dt9920001557
• 作为产物：
  描述：

  tetrakis(acetonitrile)copper(I) perchlorate 、 N,N'-bis-(2-(phenylmethylthio)benzylidene)-1,2-diaminoethane 以 乙醇 为溶剂， 以90%的产率得到N,N'-bis{(2-(phenylmethylthio)phenyl)methylene}ethane-1,2-diaminecopper(I) perchlorate
  参考文献：
  名称：

  Crystal structures, dynamic behaviour and electrochemical properties of the copper-(I) and -(II) complexes of a new N2S2 ligand

  摘要：

  The complexing properties of the new quadridentate N2S2 ligand N,N'-bis{[2-(phenylmethylthio)phenyl]methylene} ethane-1,2-diamine, L, with Cu(I) and Cu(II) have been investigated. The perchlorate salt of [CuL]+ occurs as orange crystals in which mirror image forms, [(+/-)-(R*,R*,S*)], of the highly distorted tetrahedral cation coexist. The CuN2-CuS2 dihedral angle = 60.0(1)-degrees, bond lengths and angles are Cu-S 2.285(1) and 2.258(1) angstrom, Cu-N 2.029(3) and 2.069(3) angstrom, N-Cu-N 82.7(1)-degrees, S-Cu-S 123.56(4)-degrees. In nitromethane solution, however, variable-temperature C-13 NMR spectroscopy indicates that [CuL]+ exists predominantly as an equilibrium mixture of the two other diastereomers, [(+/-)-(R*,R*,R*)] and [(+/-)R*, S*,S*)] for which the interconversion barrier corresponds to DELTA-G280 = 59.8 +/- 0.6 kJ mol 1. Exposure of an ethanolic solution of [CuL]ClO4 to the atmosphere leads to slow deposition of brown crystals of [CuL(H2O)][ClO4]2. Crystal structure determination revealed the Cu(II) cation to be square-pyramidal with the water molecule occupying the apical position: Cu-S 2.323(6) and 2.318(5) angstrom; Cu-N 1.94(1) and 2.00(2) angstrom; Cu-O (H2O) 2.29(1) angstrom. The crystals are achiral and racemic, arising through coexistence of the [(+/-)-(R*,R*)] enantiomeric forms of the complex. Cyclic voltammetry indicates a quasi-reversible system for which E1/2 = 0.28 V vs. saturated calomel electrode.

  DOI：

  10.1039/dt9920001557

文献信息

• Structural, spectroscopic and electrochemical consequences of displacing the co-ordinated thioethers from a copper(I) N2S2 complex
  作者：David A. Nation、Max R. Taylor、Kevin P. Wainwright

  DOI：10.1039/dt9920002411

  日期：——

  The effect of detaching the two co-ordinated thioethers from the copper(I) N2S2 complex N,N′-bis[2-(phenylmethylthio)phenyl]methylene}ethane-1,2-diaminecopper(I) perchlorate, [CuL]ClO4, has been investigated. This has been achieved by treating this complex with a second mole of the same ligand such that CuI becomes co-ordinated to two ligands, each by way of its diimine moiety. The resulting orange

  从铜（拆卸两个协调硫醚的效果我）N 2小号2复杂Ñ，Ñ ' -双[2-（苯基甲硫基）苯基]亚甲基}乙烷-1,2- diaminecopper（我），高氯酸已经研究了[CuL] ClO 4。这是通过用第二摩尔相同的配体处理该配合物而实现的，使得Cu I配位至两个配体，每个配体都通过其二亚胺部分。生成的橙色络合物[CuL 2 ] ClO 4在固态下是空气稳定的。X射线晶体结构分析结果表明，该阳离子具有近似四面体的立体化学结构，CuN 2 –CuN 2二面角为90.7（4）°，Cu–N键长均为2.05（1）Å，且螯合物为N–Cu–N角度为83.9（4）和85.0（4）°。从循环伏安法的结果表明在Cu的准可逆性我↔的Cu II电子转移过程中，和0.23±0.02伏的标准还原电势相对于饱和甘汞电极。铜（II）物种的化学分解也很明显，这与尝试直接合成时其高反应活性是一致的。