diaquonickel(III) 1,4,8,11-tetraazacyclotetradecane | 72360-42-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 金属杂环化合物
• 英文名称: diaquonickel(III) 1,4,8,11-tetraazacyclotetradecane
• 英文别名: Ni(1,4,8,11-tetraazacyclotetradecane)(H2O)2(3+)
• CAS: 72360-42-0
• 化学式: C₁₀H₂₈N₄NiO₂
• 分子量: 295.048
• InChiKey: XWOUTCWNXBMLLN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  diaquonickel(III) 1,4,8,11-tetraazacyclotetradecane 在 对甲苯磺酸 作用下， 生成 nickel(II) 1,4,8,11-tetraazacyclotetradecane
  参考文献：
  名称：

  使用61 Ni esr和马库斯互相关反应测量的Ni II cyclam 2+ / Ni II cyclam 3+的自交换反应速率

  摘要：

  标记的[Ni III 1,4,8,11-四氮杂环十四烷] 3+（61 Ni，I = ）配合物的电子共振光谱已用于确定Ni II-和Ni III -tetra之间电子交换的一级速率-azamacrocycle复合物；基于Fe III（三-聚吡啶）配合物反应的独立测量提供了更准确的自交换参数值。

  DOI：

  10.1039/c39820000274
• 作为产物：
  描述：

  nickel(II) 1,4,8,11-tetraazacyclotetradecane 、 [(1,4,8,11-tetraazacyclotetradecane)diaquanickel(II)] 在 水 作用下， 以 高氯酸 为溶剂， 生成 diaquonickel(III) 1,4,8,11-tetraazacyclotetradecane
  参考文献：
  名称：

  Yao, Qin; Bakac, Andreja; Espenson, James H., Inorganic Chemistry, 1993, vol. 32, # 8, p. 1488 - 1492

  摘要：

  DOI：

文献信息

• Entropy contribution to the relative solution stability of copper(III) and nickel(III) tetraazamacrocyclic complexes in aqueous perchloric acid
  作者：Giancarlo De Santis、Luigi Fabbrizzi、Maurizio Licchelli、Piersandro Pallavicini

  DOI：10.1039/dt9910002925

  日期：——

  changes determined. The potential difference, ECu–ENi, which is related to the metathetic equilibrium [CuIIIL]3++[NiIIL]2+⇌[CuIIL]2++[NiIIIL]3+, becomes less positive with increasing HClO4 concentration, indicating a stabilizing effect on the copper(III) complex, compared to NiIII. This effects is related to the competition by the ions of the electrolyte for the water molecules co-ordinated to the electroactive

  包含等摩尔量的不同浓度HClO 4（[Ni II（cyclam）] [ClO 4 ] 2和[Cu II（cyclam）] [ClO 4 ] 2（cyclam = 1,4,8,11-四氮杂环十四烷）的溶液通过伏安法研究了4–11.56 mol dm –3），并确定了与Ni II –Ni III和Cu II –Cu III氧化还原变化有关的电势。电位差E Cu – E Ni与复分解平衡有关[Cu III L]3+ + [Ni II L] 2+ + [Cu II L] 2+ + [Ni III L] 3+，随着HClO 4浓度的增加，正值变小，表明与铜（ III）配合物相比有稳定作用镍三。该效应与电解质的离子竞争与电活性物质配位的水分子的竞争有关。熵变Δ小号⊖与复分解平衡相关联的通过伏安调查确定在不同的温度（-15至+ 40℃）进行。在Δ的基础上小号⊖值表明，在HClO 4浓度低于8 mol dm
• Effect of Conformational Constraints on Gated Electron-Transfer Kinetics. A Multifaceted Study on Copper(II/I) Complexes with cis- and trans-Cyclohexanediyl-[14]aneS4
  作者：Cynthia A. Salhi、Qiuyue Yu、Mary Jane Heeg、Nicole M. Villeneuve、Kerri L. Juntunen、Ronald R. Schroeder、L. A. Ochrymowycz、D. B. Rorabacher

  DOI：10.1021/ic00128a016

  日期：1995.11

  A multifaceted study has been conducted on the electron-transfer reactions of the copper(II/I) complexes formed with 2,3-cis- and 2,3-trans-cyclohexanediyl-1,4,8,11-tetrathiacyclotetradecane (designated as cis- and tmns-cyhx-[14]aneS(4)). Each system has been studied by (i) H-1-NMR line broadening in D2O to determine the electron self-exchange rate constants at zero driving force, (ii) rapid-scan cyclic voltammetry in 80% methanol-20% water (w/w) to determine the rate constants for conformational changes and heterogeneous electron transfer, and (iii) stopped-flow spectrophotometry using a total. of eight oxidizing and reducing counterreagents to determine the cross-reaction electron-transfer rate constants from which self-exchange rate constants can be calculated for various driving forces. The crystal structures of both Cu(II)L complexes and of Cu-I(trans-cyhx-[14]aneS(4)) have also been determined. From the NMR measurements, the electron self-exchange rate constants have been evaluated [at 25 degrees C, mu = 0.10 M (NO3-)] as k(11(ex)) = (5.0 +/- 0.5) x 10(4) and less than or equal to 10(3) M(-1) s(-1) for Cd-II/I(cis-) and Cu-II/I(trans-cyhx-[14]aneS(4)), respectively. Application of the Marcus relationship to the numerous cross-reaction rate constants yields variable behavior which is consistent with a dual-pathway mechanism for which the following self-exchange rate constants have been resolved [25 degrees C, mu = 0.10 M (ClO4-)]: for Cu-II/I(cis-cyhx-[14]aneS(4)), k(11(A)) = 5 x 10(4), k(11(B)) less than or equal to 10 M(-1) s(-1); for Cu-II/I(trans-cyhx-[14]aneS(4)), k(11(A)) = 2 x 10(3), k(11(B)) less than or equal to 10 M(-1) s(-1). The reduction reactions proceed by the most favorable pathway (pathway A) involving a metastable Cu(I)L intermediate (P) while the limiting oxidation reactions proceed by an alternate pathway (pathway B) involving a less stable Cu(II)L intermediate (Q). The change in pathway is mediated by the rate constant (k(RP)) for the formation of the Cu(I)L(P) intermediate from the stable Cu(I)L(R) complex. This latter rate constant has been estimated from both cyclic voltammetric measurements (CV, 80% methanol) and Cu(I)L homogeneous oxidation kinetics (Ox, H2O) as follows [25 degrees C]: for Cu-I(cis-cyhx-[14]aneS(4)), k(RP) = 4.4 x 10(2) (CV) and 1.1 x 10(2) s(-1) (Ox); for Cu-I(trans-cyhx-[14]aneS(4)), k(RP) = 1.5 x 10(2) (CV) and 32 s(-1) (Ox). The values obtained from homogeneous oxidations are believed to be the more reliable. The crystal structures reveal that both Cu(II)L complexes are square pyramidal with the four sulfur donor atoms occupying the basal plane and a coordinated water molecule (or anion) at the apex. The Cu-I(trans-cyhx-[14]aneS(4)) complex is in a flattened tetrahedral geometry in which all four sulfur donor atoms remain coordinated. These structures imply that, for each Cu(III)L system, two sulfur donor atoms must invert during the overall electron-transfer process. It is postulated that these donor atom inversions may represent the primary barrier for the conformational change represented in the R --> P step.The self-exchange rate constant representative of the electron-transfer step itself, corrected for the separate conformational change step, is estimated to be on the order of 10(6) M(-1) s(-1) for both systems, equivalent to the largest self-exchange rate constants known for rigid Cu(II/I)L systems. Crystal data [Mo K alpha radiation (lambda = 0.710 73 Angstrom)] are as follows. For [Cu-II(cis-cyhx-[14]aneS(4))(H2O)](ClO4)(2) (1): CuS4C14H28Cl2O9, triclinic system, space group P $(1) over bar$$, a = 9.734(4) Angstrom, b = 10.155(3) Angstrom, c = 13.058(4) Angstrom, alpha = 91.73(2)degrees, beta = 91.52(3)degrees, gamma = 117.75(3)degrees, V = 1140.6(7) Angstrom(3), Z = 2, R = 0.049, R(w) = 0.050, T = -110 degrees C. For [Cu-II(trans-cyhx-[14]aneS(4))(H2O)](ClO4)(2) (2a): CuS4Cl4H28Cl2O9, triclinic system, space group P $(1) over bar$$, a = 9.177(5) Angstrom, b = 10.641(5) Angstrom, c = 13.037(4) Angstrom, alpha = 87.26(3)degrees, beta = 88.13(4)degrees, gamma = 69.19(3)degrees, V = 1188.5(8) Angstrom(3), Z = 2, R = 0.050, R(w) = 0.056, T = -110 degrees C. For [Cu-II(trans-cyhx-[14]aneS(4))Cl]. 1/2CuCl(4) . H2O (2b): Cu1.5C14H28S4Cl3O, orthorhombic system, space group Pbcn, a = 28.206(7) Angstrom, b = 10.115(3) Angstrom, c = 14.707(2) Angstrom, V = 4196(2) Angstrom(3), Z = 8, R = 0.038, R(w) = 0.042, T = 22 degrees C. For [Cu-I(trans-cyhx-[14] aneS(4))]ClO4 . 1/4H(2)O (3): CuS4C14H26.5ClO4.25, monoclinic system, space group P2(1)/n, a = 10.135(2) Angstrom, b = 16.044(2) Angstrom, c = 12.675(2) Angstrom, beta = 105.10(1)degrees, V = 1989.9(5) Angstrom(3), Z = 4, R = 0.038, R(w) = 0.038, T = -110 degrees C.
• Haines, Robert I.; McAuley, Alexander, Inorganic Chemistry, 1980, vol. 19, # 3, p. 719 - 723
  作者：Haines, Robert I.、McAuley, Alexander

  DOI：——

  日期：——