chloro[1-(2-mercapto-2-methylpropyl)-methyl-1,4-diazacycloheptane]nickel(II) | 1174551-24-6

• 英文名称: chloro[1-(2-mercapto-2-methylpropyl)-methyl-1,4-diazacycloheptane]nickel(II)
• 英文别名: [(1-(2-mercapto-2-methylpropyl)methyl-1,4-diazacycloheptane)NiCl]2
• CAS: 1174551-24-6
• 化学式: C₂₀H₄₂Cl₂N₄Ni₂S₂
• 分子量: 590.998
• InChiKey: VONQYEGQJPBJAX-UHFFFAOYSA-J

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

• 作为反应物：
  描述：

  咪唑 、 chloro[1-(2-mercapto-2-methylpropyl)-methyl-1,4-diazacycloheptane]nickel(II) 以 甲醇 为溶剂， 以71%的产率得到[1-(2-mercapto-2-methylpropyl)-methyl-1,4-diazacycloheptane]nickel(II) imidazole chloride hydrate
  参考文献：
  名称：

  Imidazole-Containing (N₃S)-Ni^II Complexes Relating to Nickel Containing Biomolecules

  摘要：

  Dimeric (N2S)Ni complexes and the monomeric N2S2 bismercaptodiazacycloheptane nickel complex, (bme-dach)Ni, serve as precursors to two N2+, N'-/S-complexes where N-2=diazacycloheptane, N'=imidazole and S=thiolate. As rare examples of nickel complexes containing a mixed thiolate/imidazole ligand set, these complexes are characterized by X-ray diffraction, UV/vis, and variable temperature H-1 NMR spectroscopies, and electrochemistry. Density functional theory computations relate the orientation of the imidazole with respect to the N2N'SNi square plane to the VT NMR observed fluxionality and activation parameters. The superoxide dismutase activity of the imidazole complexes was investigated by the nitroblue tetrazolium assay.

  DOI：

  10.1021/ic900778k
• 作为产物：
  描述：

  nickel(II) chloride hexahydrate 、 1-(2-mercapto-2-methylpropyl)-methyl-1,4-diazacycloheptane 在 MeONa 作用下， 以 甲醇 为溶剂， 生成 chloro[1-(2-mercapto-2-methylpropyl)-methyl-1,4-diazacycloheptane]nickel(II)
  参考文献：
  名称：

  Imidazole-Containing (N₃S)-Ni^II Complexes Relating to Nickel Containing Biomolecules

  摘要：

  Dimeric (N2S)Ni complexes and the monomeric N2S2 bismercaptodiazacycloheptane nickel complex, (bme-dach)Ni, serve as precursors to two N2+, N'-/S-complexes where N-2=diazacycloheptane, N'=imidazole and S=thiolate. As rare examples of nickel complexes containing a mixed thiolate/imidazole ligand set, these complexes are characterized by X-ray diffraction, UV/vis, and variable temperature H-1 NMR spectroscopies, and electrochemistry. Density functional theory computations relate the orientation of the imidazole with respect to the N2N'SNi square plane to the VT NMR observed fluxionality and activation parameters. The superoxide dismutase activity of the imidazole complexes was investigated by the nitroblue tetrazolium assay.

  DOI：

  10.1021/ic900778k

文献信息

• Orientation and Stereodynamic Paths of Planar Monodentate Ligands in Square Planar Nickel N₂S Complexes
  作者：Roxanne M. Jenkins、Michael L. Singleton、Lauren A. Leamer、Joseph H. Reibenspies、Marcetta Y. Darensbourg

  DOI：10.1021/ic1002012

  日期：2010.6.21

  pocket. In the case of the imidazole ligands a minor electronic contribution derives from intramolecular electrostatic interactions (imidazole C-2 C−Hδ+- - Sδ− interaction). Computational studies find this donor−acceptor interaction is magnified in O-analogues, predicting coplanar arrangements in the ground state of N2ONimidNi complexes.

  组氨酸供体在含 Ni 生物分子的结合位点中的公认存在促进了对与平面 N 2 SNi 部分结合的平面单齿配体（L = 咪唑、吡啶和N-杂环卡宾）的定向偏好和立体动力学性质的研究。方形平面[N 2 SNiL] n +复合物通过二聚体硫醇盐-S桥接的[N 2 SNi] 2复合物的桥裂反应获得。三个单核产物和三个单硫醇桥接二镍配合物的固态分子结构表明，添加的单齿配体的平面取向很大程度上垂直于 N 2SNiL 方形平面。动态过程的变温1 H NMR 表征和咪唑配合物在其停止交换限制光谱中的基态异构体比率，很容易与密度泛函理论 (DFT) 指导的 Ni-L 旋转激活障碍的解释相关联。完整的 DFT 表征发现 Ni-L 键延长以及过渡态中的四面体扭曲变形，在 NHC 复合物中达到最大值，并且主要与源自配体和结合口袋的空间位阻有关。在咪唑配体的情况下，较小的电子贡献来自分子内静电相互作用（咪唑 C-2 C-H