6,6'-C-spirobi(1,4,8,11-tetraazacyclotetradecane) | 109356-09-4

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 6,6'-C-spirobi(1,4,8,11-tetraazacyclotetradecane)
• 英文别名: 6,6'-spiro-bi(cyclam)；2,5,9,12,16,19,23,26-Octaazaspiro[13.13]heptacosane；2,5,9,12,16,19,23,26-octazaspiro[13.13]heptacosane
• CAS: 109356-09-4
• 化学式: C₁₉H₄₄N₈
• 分子量: 384.612
• InChiKey: VBYBLNVYWLNCBW-UHFFFAOYSA-N

物化性质

• 沸点：
  589.5±50.0 °C(Predicted)
• 密度：
  1.05±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -2.8
• 重原子数：
  27
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  96.2
• 氢给体数：
  8
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  copper(II) perchlorate 、 6,6'-C-spirobi(1,4,8,11-tetraazacyclotetradecane) 在 NaHCO₃ 、 C₂H₅OH 作用下， 以 乙醇 为溶剂， 生成
  参考文献：
  名称：

  Coordination polymerisation of a binuclear copper(II) macrocyclic cation through self-assembly

  摘要：

  新制备的双核阳离子 [Cu2Cl(L)]3+[L= 6,6′-spiro-bi(cyclam) where cyclam = 1,4,8,11-tetraazacyclotetradecane] 自组装成 µ-氯桥一维聚合物；报告了晶体结构和初步光谱特征。

  DOI：

  10.1039/c39920001321
• 作为产物：
  描述：

  1,3-二碘-2,2-双(碘甲基)丙烷 在 四氢呋喃 、 硼烷 作用下， 以 乙醇 为溶剂， 反应 99.0h， 生成 6,6'-C-spirobi(1,4,8,11-tetraazacyclotetradecane)
  参考文献：
  名称：

  McAuley, A.; Beveridge, K.; Subramanian, S., Canadian Journal of Chemistry, 1989, vol. 67, p. 1657 - 1665

  摘要：

  DOI：

文献信息

• Stepwise Complexation of Ni(II) and Cu(II) Ions by 6,6‘-C-spirobi(cyclam) (cyclam = 1,4,8,11-Tetraazacyclotetradecane), L₁. Syntheses and Redox Chemistry of [M(H₂L₁)]X₄ (M = Cu²⁺, Ni²⁺), [Cu₂(L₁)]X₄, and [CuNi(L₁)]X₄ (X = ClO₄^-) and the X-ray Crystal Structure of [Cu₂(L₁)](ClO₄)₄
  作者：A. McAuley、S. Subramanian、M. J. Zaworotko、K. Biradha

  DOI：10.1021/ic9904844

  日期：1999.11.1

  (cyclam = 1,4,8,11-tetraazacyclotetradecane), complexes Cu(2+) and Ni(2+) ions in a stepwise fashion to form [M(H(2)L(1))](ClO(4))(4) (M = Cu(2+) and Ni(2+)) from which [CuNi(L(1))](ClO(4))(4) has been prepared selectively. The preparation and the structure of [Cu(2)(L(1))](ClO(4))(4) (empirical formula, C(19)H(44)N(8)Cu(2)Cl(4)O(16); space group, triclinic; P&onemacr;; a = 8.1815(6) Å, b = 12.6098(9)

  在HClO（4）水溶液中，阳离子[H（4）（L（1））]（4+），其中L（1）为6,6'-C-spirobi（cyclam）（cyclam = 1,4,8 ，11-四氮杂环十四烷），Cu（2+）和Ni（2+）离子逐步形成[M（H（2）L（1））]（ClO（4））（4）（M =选择性地制备了[CuNi（L（1））]（ClO（4））（4）的Cu（2+）和Ni（2+））。[Cu（2）（L（1））]（ClO（4））（4）的制备和结构（经验公式，C（19）H（44）N（8）Cu（2）Cl（4 ）O（16）;空间群，三斜; P＆onemacr ;; a = 8.1815（6）Å，b = 12.6098（9）Å，c = 16.6565（12）Å，alpha = 80.3890（10）度，beta = 76.5840（ 10）度，gamma = 87.1750（10）度，V = 1647.9（2）Å（3）和Z
• Synthesis and X-ray crystal structure of a C-spiro-bi-[cyclam nickel(II)] complex (cyclam = 1,4,8,11-tetra-azacyclotetradecane)
  作者：A. McAuley、S. Subramanian、T. W. Whitcombe

  DOI：10.1039/c39870000539

  日期：——

  salt 6,6′-spirobi[1,4,8,11-tetra-azacyclotetradecane]nickel(II) tetraperchlorate C-spiro-bi-[cyclam nickel(II)]} was isolated as single crystals and the X-ray crystal structure obtained; a deviation in orthogonality of the macrocyclic rings, resulting in possible Ni–Ni interaction, is deduced from the e.s.r. spectra of the oxidised forms of the complex.

  盐6,6'-螺二[1,4,8,11-四- azacyclotetradecane]镍（II）tetraperchlorate C螺双环[cyclam镍（II）]}，分离单晶和X -获得射线晶体结构；从配合物的氧化形式的esr光谱推论出大环的正交性偏差，可能导致Ni-Ni相互作用。
• Synthesis, Spectroscopy, and Redox Behavior of the Binuclear Complex Cation [Ni₂(6,6‘-spirobi(cyclam))]⁴⁺ (cyclam = 1,4,8,11-Tetraazacyclotetradecane):  Characteristics of a Transient Ni(II)−Ni(III) Species
  作者：A. McAuley、S. Subramanian

  DOI：10.1021/ic970327+

  日期：1997.11.1

  The homobinuclear cation [Ni-2(L-1)](4+) (L-1 = 6,6'-C-spirobi(cyclam)), in which the nitrogen donors adopt a trans-III configuration, has been synthesized, and its redox behavior has been investigated by electrochemical, spectroscopic, and kinetic methods. Cyclic voltammetry in aqueous media ([H+] = 0.1 and 1.0 M in LiNO3/LiClO4/CF3SO3Li) shows a single wave (Delta E-p = 58 mV). With the gradual addition of LiCl/Li2SO4, this wave is shifted cathodically. Simultaneously, the value of Delta E-p also gradually decreases from 58 to 37 mV in 1.0 M chloride and to 42 mV in 0.75 M sulfate media. Similar trends are also noticed in linear df voltammograms. [Ni-2(L-1)](ClO4)(4) in CH3CN ([TEAP] = 1.0 M; E-1/2(1) = 0.735 V and E-1/2(2) = 0.835 V vs Fc/Fc(+)) and [Ni-2(L-1)]Cl-4 in CH3Cl2 ([TEAC] = 0.1 M; E-1/2(1) = 0.640 V and E-1/2(2) = 0.766 V vs Fc/Fc(+)) media show two overlapping waves, In nitromethane, the redox process is complicated by adsorption. Because of the very small difference in redox potentials, the selective oxidation of one of the Ni(II) centers to form a mixed-valent Ni(II)-Ni(III) species is not practical. However, during reductive decomposition of the his-Ni(LII) species, a mixed-valent species could be identified. In stopped flow kinetics experiments, the UV-visible spectrum of a transient Ni(II)-Ni(III) intermediate in acetonitrile has been elucidated by one-electron reduction of the bis-Ni(III) species with [Ni-II(9-aneN(3))(2)](2+) (9-aneN(3) = 1,4,7-triazacyclononane). The differences in the redox behavior in various media are explained in terms of electrostatic interactions between the adjacent nickel centers influenced by sterically controlled axial ligation of counterions and solvents. Evidence for changes in coordination geometry in Ni(II) and Ni(III) species obtained from UV-vis and ESR studies is also presented.
• McAuley, A.; Beveridge, K.; Subramanian, S., Canadian Journal of Chemistry, 1989, vol. 67, p. 1657 - 1665
  作者：McAuley, A.、Beveridge, K.、Subramanian, S.、Whitcombe, T. W.

  DOI：——

  日期：——
• Coordination polymerisation of a binuclear copper(II) macrocyclic cation through self-assembly
  作者：A. McAuley、S. Subramanian、Michael J. Zaworotko

  DOI：10.1039/c39920001321

  日期：——

  The newly prepared binuclear cation [Cu2Cl(L)]3+[L= 6,6′-spiro-bi(cyclam) where cyclam = 1,4,8,11-tetraazacyclotetradecane] self-assembles into a µ-chloro-bridged one-dimensional polymer; the crystal structure and preliminary spectroscopic features are reported.

  新制备的双核阳离子 [Cu2Cl(L)]3+[L= 6,6′-spiro-bi(cyclam) where cyclam = 1,4,8,11-tetraazacyclotetradecane] 自组装成 µ-氯桥一维聚合物；报告了晶体结构和初步光谱特征。