copper(II) 1,4,8,11-tetrazacyclotetradecane dichloride | 951329-67-2

• 分子结构分类: 有机化合物 - 有机金属化合物
• 英文名称: copper(II) 1,4,8,11-tetrazacyclotetradecane dichloride
• 英文别名: Cu(cyclam)Cl₂；dichlorocopper;1,4,8,11-tetrazacyclotetradecane
• CAS: 951329-67-2
• 化学式: C₁₀H₂₄Cl₂CuN₄
• 分子量: 334.779
• InChiKey: LODAWFNEQIBYIM-UHFFFAOYSA-L

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：

  copper(II) 1,4,8,11-tetrazacyclotetradecane dichloride 、 [U(3,5-dimethylpyrazolate)4]2*0.5PhMe 以 二氯甲烷 为溶剂， 生成 (1,4,8,11-tetraazacyclotetradecane)Cu[(μ-Cl)U(3,5-dimethylpyrazolate)4]2
  参考文献：
  名称：

  Magnetic Exchange Coupling in Chloride-Bridged 5f−3d Heterometallic Complexes Generated via Insertion into a Uranium(IV) Dimethylpyrazolate Dimer

  摘要：

  The homoleptic dimer complex [U(Me(2)PZ)(4)](2) (Me(2)PZ- = 3,5-dimethylpyrazolate) was obtained upon reacting UCl4 with KMe(2)PZ in THF, followed by extraction into toluene. The structure of the dimer consists of two U-IV centers, each coordinated in a pseudo trigonal bipyramidal geometry, connected through two bridging Me(2)Pz(-) ligands. Bases are capable of cleaving the dimer; for example, reaction with THF affords the mononuclear complex (Me(2)PZ)(4)U(THF). More importantly, the dimer can be cleaved via insertion of terminal chloride ligands, such that reactions with (cyclam)MCl2 (M = Ni, Cu, Zn; cyclam = 1,4,8,11-tetraazacyclotetradecane) in dichloromethane generate the linear, chloride-bridged clusters (cyclam)M[((sic)Cl-L)U(Me(2)Pz)(4)](2). variable temperature magnetic susceptibility data were collected for all three clusters to probe any possible magnetic exchange coupling. The data for the cluster centered by an S = 0 Zn-II ion exhibit behavior typical of UIV complexes, with chi T-M decreasing steadily as the temperature drops. Data for the CuU2 cluster show a parallel variance with temperature, indicating the absence of any magnetic exchange coupling. In contrast, subtracting the ZnU2 data from the NiU2 data exposes a rise in chi T-M with decreasing temperature, suggesting weak ferromagnetic coupling between the Ni-II (S = 1) and U-IV centers. Employing a simple spin-only exchange model, a lower bound for the coupling constant was estimated at J = 2.3 cm(-1). Consistent with a simple superexchange mechanism for the coupling, density functional theory calculations performed on a [(Me(2)Pz)(4)UCl](-) fragment of the cluster show the spin to reside in 5f(xyz) and 5f(Z) (x 2(-y) (2)) orbitals, exhibiting delta symmetry with respect to the U-Cl bond. Low-temperature magnetization data collected for NiU2 suggest the presence of a large axial zero-field splitting; however, ac magnetic susceptibility experiments gave no indication of single-molecule magnet behavior.

  DOI：

  10.1021/ja0725044
• 作为产物：
  描述：

  1,4,8,11-四氮杂环十四烷 、 copper dichloride 在 盐酸 、 potassium hydroxide 作用下， 以 水 为溶剂， 以74%的产率得到copper(II) 1,4,8,11-tetrazacyclotetradecane dichloride
  参考文献：
  名称：

  C-功能化仙客来与铜 (II) 和锌 (II) 的络合：与亲本仙客来类似物相比的相似性和变化

  摘要：

  在此，我们报告了先前报道的配体cyclam、CB-cyclam、TMC、DMC和CB-DMC及其C功能类似物cyclam-E、CB-cyclam-E、TMC-E、DMC的综合协调研究-E和CB-DMC-E。这组配体包括环菌素、交叉桥联的环菌素，它们的二甲基化或四甲基化衍生物，以及在环的一个 β-N 位上带有额外羟乙基的类似物。这些大环化合物的 Cu(II) 和 Zn(II) 配合物之前已经被强调为生物学兴趣，但它们在固态和溶液中的结构细节在很大程度上仍未被探索。我们特别分析了添加非配位N-甲基和C-羟乙基官能团在配合物的结构中具有。使用单晶 X 射线衍射和核磁共振、电子吸收和 EPR 光谱以及 DFT 研究合成并研究了所有 Cu(II) 和 Zn(II) 配合物。还进行了酸性条件下的解离动力学实验和电化学研究。特别注意分析溶液和固态中存在的不同构型，以及C附加的羟乙基对配位行为的影响。根据

  DOI：

  10.1021/acs.inorgchem.1c01572