(1,4,8,11-tetraazacyclotetradecane)copper(II) ion | 21780-12-1

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: (1,4,8,11-tetraazacyclotetradecane)copper(II) ion
• 英文别名: (1,4,8,11-tetraazacyclotetradecane)copper(II)(2+)；Cu(1,4,8,11-tetraazacyclotetradecane)(2+)；[Cu(cyclam)]²⁺；Cu(II)(rel-(1R,4R,8S,11S)1,4,8,11-tetra-azacyclotetradecane)；copper;1,4,8,11-tetrazacyclotetradecane
• CAS: 21780-12-1
• 化学式: C₁₀H₂₄CuN₄
• 分子量: 263.873
• InChiKey: PFFRGXSRPUXLRK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.86
• 重原子数：
  15
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  48.1
• 氢给体数：
  4
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (1,4,8,11-tetraazacyclotetradecane)copper(II) ion 在 sodium nitrate 、 硝酸 作用下， 以 硝酸 为溶剂， 生成 Cu(Hcyclam)(3+)
  参考文献：
  名称：

  Chen, Lien-Huei; Chung, Chung-Sun, Inorganic Chemistry, 1988, vol. 27, # 11, p. 1880 - 1883

  摘要：

  DOI：
• 作为产物：
  描述：

  Cu(4-azaheptane-1,7-diamine)(2+) 以 水 为溶剂， 生成 (1,4,8,11-tetraazacyclotetradecane)copper(II) ion
  参考文献：
  名称：

  具有大环配体的金属配合物。第二十一部分。Cu 2+配合物的稳定性与其与1,4,8,11-四氮杂环十四烷† ‡的络合速率之间的非线性关系

  摘要：

  1,4,8,11-四氮杂十四烷（Cy）与一系列Cu（II）配合物之间的反应动力学（1）CuL（L）=乙醇酸，丙二酸，琥珀酸，吡啶甲酸，甘氨酸，亚氨基二乙酸酯，次氮基三乙酸酯，N -（2-羟乙基）乙二胺三乙酸酯，乙二胺，1，3-二氨基丙烷，二亚乙基三胺和N，N-双（3-氨基丙胺）在25°和I = 0.5（KNO 3）上进行分光光度法研究。通过分析在不同pH值下获得的log k obs / log [L]曲线，可解析双分子速率常数k （表3）通过非线性曲线拟合程序获得。对于几乎所有研究的系统，均获得了速率常数k，该常数描述了1：1复杂CuL与大环CyH单质子化形式之间的反应。讨论了log k和log K CuL之间的非线性关系及其性质。结果表明，其他人描述的反应性和稳定性之间的反比关系只是更一般的方程式的一种特殊情况。这里描述3。

  DOI：

  10.1002/hlca.19850680613

文献信息

• Formation kinetics of pendant arm polyamine macrocycles with copper(II)†
  作者：Peter G. Lye、Geoffrey A. Lawrance、Marcel Maeder

  DOI：10.1039/b102845f

  日期：——

  The complexation reaction between Cu(II) and a series of cyclam analogue macrocycles with dangling primary amine groups was investigated in aqueous solution. The pH dependence of the reaction was measured between pH 0 and 5.5 covering a range of different protonation stages of the ligands. The kinetics was observed by stopped-flow measurements followed at many wavelengths. An initial second order reaction results in an intermediate which isomerises to a stable complex. The observed rate constants for the initial step varied between 1.5 × 10−2 M−1 s−1 at pH 0 and 6.3 × 105 M−1 s−1 at pH 5.3; for the secondary step the rates varied between 2 × 10−4 s−1 at pH 1 and 24 s−1 at pH 5.3. The pH dependence was successfully analysed in terms of the different reactivities for differently protonated ligands for the first step and differently protonated complexes for the second step. Ligands with unprotonated dangling primary amines react with rate constants of 106–107 M−1 s−1, the rates drop dramatically upon protonation of the arms to ca. 10–102 M−1 s−1 which are very similar to the rates of the parent cyclam ligand of equivalent protonation. The pH dependence of the secondary isomerisation reaction is explained in similar ways: protonated, dangling arms inhibit the isomerisation reaction completely.

  研究了水溶液中 Cu(II) 与一系列带有悬浮伯胺基团的环胺类似大环之间的络合反应。在 pH 值 0 至 5.5 之间测量了反应的 pH 依赖性，涵盖了配体的不同质子化阶段。通过多种波长的停流测量观察了反应动力学。最初的二阶反应会产生一个中间产物，该中间产物会异构为一个稳定的复合物。观察到的初始步骤的速率常数在 pH 值为 0 时为 1.5 × 10-2 M-1 s-1 和 pH 值为 5.3 时为 6.3 × 105 M-1 s-1 之间变化；次级步骤的速率在 pH 值为 1 时为 2 × 10-4 s-1 和 pH 值为 5.3 时为 24 s-1 之间变化。根据第一步中不同质子化配体和第二步中不同质子化配合物的不同反应活性，成功地分析了 pH 依赖性。未质子化悬空伯胺配体的反应速率常数为 106-107 M-1 s-1，当臂质子化时，反应速率急剧下降至约 10-102 M-1 s-1，与质子化程度相当的母环胺配体的反应速率非常相似。二级异构化反应的 pH 值依赖性也有类似的解释：质子化的悬臂完全抑制了异构化反应。
• Comparative study of the electrochemical and pulse-radiolytic oxidation of the complexes of nickel(II) and copper(II) containing 1,4,8,11-tetra-azacyclotetradecane
  作者：Esther Zeigerson、Gregory Ginzburg、Dan Meyerstein、Louis J. Kirschenbaum

  DOI：10.1039/dt9800001243

  日期：——

  have been studied in aqueous acidic perchlorate and sulphate media. As with other nickel macrocyclic systems, [Ni(cyclam)]2+ is oxidized to NiIII, the stability of which is enhanced by sulphate complexation. In contrast, [Cu(cyclam)]3+ is much less stable than the nickel analogue and does not form a stable sulphate complex. Electrochemical oxidation of [Cu(cyclam)]2+ at pH 1.6 is a multistep process which

  在酸性高氯酸盐和硫酸盐介质中研究了[Ni（cyclam）] 2+和[Cu（cyclam）] 2+（cyclam = 1,4,8,11-四氮杂环十四烷）的电化学和脉冲辐射氧化。与其他镍大环系统一样，[Ni（cyclam）] 2+被氧化为Ni III，硫酸盐络合可提高其稳定性。相反，[Cu（cyclam）] 3+的稳定性比镍类似物差得多，并且不形成稳定的硫酸盐络合物。pH值为1.6时[Cu（cyclam）] 2+的电化学氧化是一个多步过程，该过程由硫酸根离子催化。该机制似乎涉及四个电子的转移，从而生成铜（II）大环二烯配合物。
• Kinetics and mechanisms of the oxidation of Ni(II) and Cu(II) macrocycles by aquasilver(II) in acidic perchlorate media
  作者：Edoardo Mentasti、Louis J. Kirschenbaum

  DOI：10.1016/s0020-1693(00)85909-5

  日期：1987.5

  1.5 × 10 4 dm 3 mol −1 s −1 for Ni II cyclam, Cu II cyclan and Cu II CT respectively, at 10 °C. While Ni III cyclam is stable enough to allow UVVis characterization, Cu III cyclam and Cu III decay by a first-order process with rate constants of 1.5 and 0.053 s −1 respectively. Reliable kinetic results could not be obtained for the oxidation of Ni II CT by silver(II), but the oxidation product does

  摘要在动力学上研究了水银（II）对Ni II cyclam，Cu II cyclam（cyclam = [18] aneN 4）和Cu II CT（CT = Me 6 [14] -4,11-dieneN 4）的氧化作用。高氯酸盐介质的范围为[HClO 4] = 1-4 mol dm -3。反应化学计量表示1 mol氧化剂与1 mol M（II）反应。停止流研究表明，对于Ni II环烷，Cu II环烷，涉及M II L + Ag 2+的单个反应路径，其中k = 2.3×10 5，3.5×10 5和1.5×10 4 dm 3 mol -1 s -1和Cu II CT分别在10°C下进行。尽管Ni III Cyclam具有足够的稳定性，可以进行UVVis表征，但Cu III cyclam和Cu III通过一级过程衰减，速率常数分别为1.5和0.053 s -1。用银（II）氧化Ni II CT
• Kinetics and mechanism of displacement of zinc(II) by copper (II) in complexes of saturated macrocyclic tetra-amines
  作者：Mutsuo Kodama、Eiichi Kimura

  DOI：10.1039/dt9800002447

  日期：——

  The kinetics of displacement of Zn2+ by Cu2+ from complexes of saturated 12- to 15-membered macrocyclic tetra-amines have been investigated in acetate-buffer solutions. Kinetic data support a common mechanism : [ZnL]2++ MeCO2H ⇌[Zn(O2CMe)]++ HL+(k1, k–1); HL++[Cu(O2CMe)]+→[CuL]2++ MeCO2H (k2), where the dissociation of L from Zn2+ is the slowest step. Values for k1 and k–1/k2 show good agreement with

  在乙酸盐-缓冲溶液中，已经研究了从饱和的12至15元大环四胺的配合物中Cu 2+置换Zn 2+的动力学。动力学数据支持的共同机制：[ZNL] 2+ +梅科2 ħ ⇌ [锌（O 2 CME）] + + HL +（ķ 1，ķ -1）; HL + + [Cu（O 2 CMe）] + → [CuL] 2+ + MeCO 2 H（k 2），其中L从Zn 2+上解离是最慢的一步。对值ķ 1和ķ -1 / ķ 2显示出良好的与以前的值一致独立地获得。讨论了k 1和k –1的激活参数。预离解机理与最近在二甲基甲酰胺溶液中卟啉络合物中类似的金属交换反应中所提出的机理相同。
• Catalytic Signal Amplification Using a Heck Reaction. An Example in the Fluorescence Sensing of Cu(II)
  作者：Qiaoyin Wu、Eric V. Anslyn

  DOI：10.1021/ja0401038

  日期：2004.11.1

  Catalytic signal enhancement using an organometallic reaction is demonstrated. The reactivity of a Heck cross-coupling reaction that creates a fluorophore is modulated by the addition of a polyazacyclam inhibitor. The inhibitor will complex with Cu(II), which restores the activity of the Pd(II). The addition of Cu(II) therefore leads to the generation of fluorescence, thereby creating a very sensitive assay for Cu(II). The rate of the Heck reaction is followed by monitoring emission as a function of time. The rate is proportional to the Cu(II) concentration and correlates to the affinity of the inhibitor to various metals. This strategy represents a general technique that can be exploited with other catalytic organometallic reactions.