dichloro(N,N-di(2-pyridylmethyl)amine)copper(II) | 51120-56-0

• 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: dichloro(N,N-di(2-pyridylmethyl)amine)copper(II)
• 英文别名: [Cu(bpa)Cl2]；[Cu(N,N-bis(picolyl)amine)Cl2]；copper;1-pyridin-2-yl-N-(pyridin-2-ylmethyl)methanamine;dichloride
• CAS: 51120-56-0
• 化学式: C₁₂H₁₃Cl₂CuN₃
• 分子量: 333.707
• InChiKey: BIPSOBXMZXTVBQ-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  -4.23
• 重原子数：
  18
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  37.8
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  Boc-Leu-bis[(2-pyridyl)methyl]amine 、 copper(II) choride dihydrate 在 methanol 作用下， 以 甲醇 为溶剂， 以53%的产率得到dichloro(N,N-di(2-pyridylmethyl)amine)copper(II)
  参考文献：
  名称：

  The Activation of Tertiary Carboxamides in Metal Complexes: An Experimental and Theoretical Study on the Methanolysis of Acylated Bispicolylamine Copper(II) Complexes

  摘要：

  It is a well-established concept that the C-N bond cleavage of carboxamide functions is facilitated by the coordination of a metal ion to the carbonyl oxygen atom. In contrast, the alternative C-N bond activation by coordination of a neutral tertiary carboxamide nitrogen atom has not been studied. We present the first results on the effect of nitrogen pyramidalization in N-coordinated metal complexes on the methanolysis of tertiary carboxamide groups. An analysis of the reactions products obtained from the methanol cleavage of [(N-Acyl-bpa)Cu](2+) (bpa = N,N-bispicolylamine) complexes is presented together with experimental and high-level theoretically calculated structures. The strong effect of different anions on the amide pyramidalization and subsequent C-N-bond cleavage is evaluated. We show that dichloro complexes [(N-Acyl-bpa)CuCl2] have much less activated amide groups than the corresponding triflate species. They should therefore be less reactive. However, [(N-Acyl-bpa)CuCl2] complexes dissociate in solution to give cationic monochloro complexes [(N-Acyl-bpa)Cu(S)Cl](+) (S = solvent molecule). Theoretical calculations show that the amide pyramidalization in the monochloro complexes is equal to that in the corresponding CF3SO3- salts. Consequently, chloro and triflato complexes are cleaved with similar rates and efficiencies. Parallels to and differences in the reactivity of purely organic distorted amides are discussed.

  DOI：

  10.1021/ic0496774

文献信息

• Metalloglycosidase Mimics: Oxidative Cleavage of Saccharides Promoted by Multinuclear Copper Complexes under Physiological Conditions
  作者：Zhen Yu、Zechariah Thompson、Shelby L. Behnke、Kevin D. Fenk、Derrick Huang、Hannah S. Shafaat、J. A. Cowan

  DOI：10.1021/acs.inorgchem.0c01193

  日期：2020.8.17

  dinuclear Cu complexes exhibit a synergistic effect and promote faster and more robust cleavage of saccharide substrates, relative to the mononuclear Cu complex, while no further enhancement is observed for the tetranuclear Cu complex. The use of scavengers for reactive oxygen species confirms that saccharide cleavage is promoted by the formation of superoxide and hydroxyl radicals through CuII/I redox chemistry

  糖类的降解与催化疗法的设计，生物燃料的生产，生物膜的抑制以及化学生物学中的其他应用有关。在这里，我们报告了能够在生理条件下裂解糖的多核铜配合物的设计。与对硝基苯基（p NP）偶联的碳水化合物的反应性研究表明，相对于单核Cu络合物，双核Cu络合物表现出协同作用，并促进了糖类底物的更快，更牢固的裂解，而四核Cu则未见进一步增强复杂。活性氧清除剂的使用证实了糖的裂解是通过铜形成超氧化物和羟基而促进的II / I氧化还原化学，类似于天然含铜裂解多糖单加氧酶（LMPO）的化学反应。二核和四核铜配合物的选择性差异不大。然而，这些是第一个报道的小的多核Cu复合物，对单糖和双糖底物表现出选择性和反应性，并为进一步开发金属糖苷酶用于化学生物学奠定了基础。
• Synthesis, superoxide dismutase, nuclease, and anticancer activities of copper(II) complexes incorporating bis(2-picolyl)amine with different counter anions
  作者：Mohamed M. Ibrahim、Abdel-Motaleb M. Ramadan、Gaber A.M. Mersal、Samir A. El-Shazly

  DOI：10.1016/j.molstruc.2011.04.009

  日期：2011.7

  reduction of nitroblue tetrazolium (NBT). The catalytic efficiency of O 2 - scavenging by complexes depends on the nature of the particular acidic anion radical incorporated in the complex molecule and follows the order: NO 3 - > ClO 4 - > Br- ⩾ Cl− > SO 4 - > AcO−. A probable mechanistic implications for the catalytic dismutation of O 2 - by copper(II) complexes are proposed. Furthermore, complex 1 exhibits

  在复合物 4-6 的情况下，建议使用单体结构中的方形平面立体化学。评估了所获得复合物的 SOD 仿生催化活性，以确定它们抑制硝基四唑 (NBT) 还原的能力。配合物清除 O 2 - 的催化效率取决于配合物分子中特定酸性阴离子自由基的性质，并遵循以下顺序：NO 3 - > ClO 4 - > Br- ⩾ Cl− > SO 4 - > AcO− . 提出了铜 (II) 配合物催化歧化 O 2 - 的可能机理。此外，在没有任何外部添加剂的情况下，复合物 1 表现出显着的基因组 DNA 水解切割。此外，
• The chemistry of nitrogen coordinated tertiary carboxamides: a spectroscopic study on bis(picolyl)amidecopper(ii) complexes
  作者：Nicole Niklas、Ralf Alsfasser

  DOI：10.1039/b516875a

  日期：——

  sampled in the aprotic solvents dichloromethane and acetonitrile, as well as under methanolysis conditions reveals the nature of several species formed in solution. The key reactions are (I) ligand exchange involving either CH3CN or CH3OH, or, in IR experiments, bromide ions from KBr, (II) coordination-dissociation equilibria involving the urethane protecting groups of amino acid substituted ligands Boc-Xaa-bpa

  叔羧酰胺的电中性氮原子的金属配位减少了CN键旋转的障碍，并使酰胺朝着甲醇分解的方向活化。X射线晶体学研究表明，该反应性与酰胺共振结构的提升和同时在氮处的锥体化有关。但是，尚未获得溶液中的机械数据。显而易见的是，结构迁移率是配合物的特征，并且晶体学数据并未完全说明相关的反应物种。在此报告中，我们总结了酰胺氮配位的双（吡啶甲基）酰胺与三氟甲磺酸铜（II）和氯化铜（II）的红外光谱，紫外可见光谱和EPR光谱。在非质子溶剂二氯甲烷和乙腈中采样的光谱之间的比较，以及在甲醇分解条件下揭示了溶液中形成的几种物质的性质。关键反应是（I）涉及CH3CN或CH3OH的配体交换，或者在IR实验中来自KBr的溴离子，（II）涉及氨基酸取代的配体Boc-Xaa-bpa（Boc ＝叔丁氧羰基，Xaa ＝分别为甘氨酸，丙氨酸和亮氨酸，bpa ＝双（吡啶甲基胺），（III）氯配体从LCuCl 2络合物中解离并形成方形-金字塔形络合物阳离子[LCuCl]