5,9,15,16-Tetramethyl-2,5,9,12-tetrazabicyclo[11.4.0]heptadeca-1(13),14,16-triene-3,11-dione | 1335200-18-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 5,9,15,16-Tetramethyl-2,5,9,12-tetrazabicyclo[11.4.0]heptadeca-1(13),14,16-triene-3,11-dione
• 英文别名: 5,9,15,16-tetramethyl-2,5,9,12-tetrazabicyclo[11.4.0]heptadeca-1(13),14,16-triene-3,11-dione
• CAS: 1335200-18-4
• 化学式: C₁₇H₂₆N₄O₂
• 分子量: 318.419
• InChiKey: VKBWZSIIEUAFKU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  23
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  64.7
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  hexaaqua iron(II) trifluoromethanesulphonate 、 5,9,15,16-Tetramethyl-2,5,9,12-tetrazabicyclo[11.4.0]heptadeca-1(13),14,16-triene-3,11-dione 在 sodium hydride 、 N,N-二甲基甲酰胺 、 氧气 作用下， 反应 3.17h， 以55%的产率得到
  参考文献：
  名称：

  酰胺基大环配体双核μ-氧化二铁(III)配合物的合成及性质

  摘要：

  我们报告了一组含有供电子和吸电子取代基的 13 元酰胺基大环配体中一系列 μ-氧化桥连二铁 (III) 配合物的合成、结构、穆斯堡尔、磁性和氧化还原表征。 –H、–Cl 和 –CH3) 位于配体外围。对于所有三种配合物，穆斯堡尔谱表明两个铁位点无法区分，X 射线晶体学结果很好地支持了这一事实。这三种配合物表现出几乎相同的异构体位移但明显不同的四重分裂值。变温磁化率测量表明，无支撑的单个 μ-氧化基团介导了两个 FeIII 离子之间的强反铁磁耦合。三个二铁配合物显示出完全不同的磁耦合（J = 191、194 和 230 cm-1，分别; Hiso = J S1·S2) 与结构差异有关。我们还表明配体上存在的给电子和吸电子取代基会影响氧化还原性能。

  DOI：

  10.1002/ejic.201200683
• 作为产物：
  描述：

  N,N'-bis(chloroacetyl)-4,5-dimethyl-o-phenylenediamine 、 N,N'-二甲基-1,3-丙二胺 在 sodium carbonate 、 lithium bromide 作用下， 以 乙腈 为溶剂， 反应 49.0h， 以33%的产率得到5,9,15,16-Tetramethyl-2,5,9,12-tetrazabicyclo[11.4.0]heptadeca-1(13),14,16-triene-3,11-dione
  参考文献：
  名称：

  Studies on the structure and properties of nickel complexes in a set of amide-based 13-membered macrocyclic ligands

  摘要：

  This work reports a systematic investigation to understand the structural, spectroscopic and redox properties of Ni(II) ion in a set of 13-membered amide-based macrocyclic ligands. Four macrocyclic ligands containing e(-)-donating/withdrawing substituents and their Ni(II) complexes have been synthesized and characterized. Structural analysis shows that the macrocyclic ligands create a square-planar environment and nicely accommodate the Ni(II) ion. Electrochemical results suggest that the complexes are capable of undergoing metal-centered oxidation. The electron-donating substituents on ligand lowers the redox potentials and better stabilizes the +3 oxidation state of metal. The electrochemically generated Ni-III species are shown to have rich spectroscopic features. For majority of complexes, the oxidized species are concluded to be NiIII by their anisotropic EPR spectra typical for Ni-III ion in square-planar geometry. The absorption and EPR spectra for nickel complex bearing an -OMe group on the ligand; however, suggest a Ni(II) complex with a ligand-based radical. (C) 2011 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2011.06.011

文献信息

• Pd(<scp>ii</scp>) complexes with amide-based macrocycles: syntheses, properties and applications in cross-coupling reactions
  作者：Sushil Kumar、Rajeev Ranjan Jha、Sunil Yadav、Rajeev Gupta

  DOI：10.1039/c4nj01300j

  日期：——

  Square-planar Pd²⁺ complexes of macrocyclic ligands carrying electronic substituents are synthesized and characterized. These well-characterized complexes have been used in the Suzuki and Heck cross-coupling reactions.

  使用带有电子取代基的大环配体的方平面Pd²⁺配合物已经被合成和表征。这些经过良好表征的配合物已经在Suzuki和Heck交叉偶联反应中被使用。
• Kumar, Sushil; Gupta, Rajeev, Indian Journal of Chemistry, Section A: Inorganic, Physical, Theoretical and Analytical, 2011, vol. 50, # 9-10, p. 1369 - 1379
  作者：Kumar, Sushil、Gupta, Rajeev

  DOI：——

  日期：——
• Studies on the structure and properties of nickel complexes in a set of amide-based 13-membered macrocyclic ligands
  作者：Savita K. Sharma、Rajeev Gupta

  DOI：10.1016/j.ica.2011.06.011

  日期：2011.10

  This work reports a systematic investigation to understand the structural, spectroscopic and redox properties of Ni(II) ion in a set of 13-membered amide-based macrocyclic ligands. Four macrocyclic ligands containing e(-)-donating/withdrawing substituents and their Ni(II) complexes have been synthesized and characterized. Structural analysis shows that the macrocyclic ligands create a square-planar environment and nicely accommodate the Ni(II) ion. Electrochemical results suggest that the complexes are capable of undergoing metal-centered oxidation. The electron-donating substituents on ligand lowers the redox potentials and better stabilizes the +3 oxidation state of metal. The electrochemically generated Ni-III species are shown to have rich spectroscopic features. For majority of complexes, the oxidized species are concluded to be NiIII by their anisotropic EPR spectra typical for Ni-III ion in square-planar geometry. The absorption and EPR spectra for nickel complex bearing an -OMe group on the ligand; however, suggest a Ni(II) complex with a ligand-based radical. (C) 2011 Elsevier B.V. All rights reserved.
• Synthesis and Properties of Dinuclear μ‐Oxodiiron(III) Complexes of Amide‐Based Macrocyclic Ligands
  作者：Sushil Kumar、Shefali Vaidya、Michael Pissas、Yiannis Sanakis、Rajeev Gupta

  DOI：10.1002/ejic.201200683

  日期：2012.11

  We report the syntheses, structural, Mossbauer, magnetic, and redox characterization of a series of μ-oxido-bridged diiron(III) complexes in a set of 13-membered amide-based macrocyclic ligands that contain electron-donating and -withdrawing substituents (–H, –Cl, and –CH3) on the ligand periphery. For all three complexes, the Mossbauer spectra indicate that two iron sites are indistinguishable, a

  我们报告了一组含有供电子和吸电子取代基的 13 元酰胺基大环配体中一系列 μ-氧化桥连二铁 (III) 配合物的合成、结构、穆斯堡尔、磁性和氧化还原表征。 –H、–Cl 和 –CH3) 位于配体外围。对于所有三种配合物，穆斯堡尔谱表明两个铁位点无法区分，X 射线晶体学结果很好地支持了这一事实。这三种配合物表现出几乎相同的异构体位移但明显不同的四重分裂值。变温磁化率测量表明，无支撑的单个 μ-氧化基团介导了两个 FeIII 离子之间的强反铁磁耦合。三个二铁配合物显示出完全不同的磁耦合（J = 191、194 和 230 cm-1，分别; Hiso = J S1·S2) 与结构差异有关。我们还表明配体上存在的给电子和吸电子取代基会影响氧化还原性能。