[Co(TC-6,6)] | 169232-87-5

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: [Co(TC-6,6)]
• CAS: 169232-87-5
• 化学式: C₂₆H₃₄CoN₄
• 分子量: 461.576
• InChiKey: VNTMPXMODRUXOD-GZOPGRJNSA-N

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：

  ferrocenium(III) tetraphenylborate 、 [Co(TC-6,6)] 以 二氯甲烷 为溶剂， 以97%的产率得到[Co(TC-6,6)](BPh₄)
  参考文献：
  名称：

  单核伪四面体钴（III）化合物的合成与表征

  摘要：

  报道了两种单核钴（III）对苯二酚和配合物[Co（TC-5,5）]（BF 4）和[Co（TC-6,6）]（BPh 4）的制备和表征。钴（III）中心以稀有的伪四面体构型存在，[Co（TC-5,5] +和[Co（TC-6,6）] +物种的扭曲角分别为65°和74° 。并与新合成的[Ga（TC-5,5）]（GaCl 4）和[Ga（TC-6,6）]（GaCl 4）类似物进行了比较，并将其电化学性质进行了比较。 TC-6,6）]（BPh 4）化合物确定为S = 2，这是自S值以来的自旋状态变化= 1发生在正方形平面和扭曲的正方形平面络合物，[CO（TC-3,3）（X）（X = BPH 4，巴' 4）和[CO（TC-4,4）] （BPh 4）。

  DOI：

  10.1021/ic5009279
• 作为产物：
  描述：

  2,9,17,24-Tetrazatricyclo[23.5.0.010,16]triaconta-1,10,12,14,16,25,27,29-octaene 、 cobalt(II) chloride 在 BuLi 作用下， 以 四氢呋喃 为溶剂， 以45%的产率得到[Co(TC-6,6)]
  参考文献：
  名称：

  Synthesis, Tuning of the Stereochemistry, and Physical Properties of Cobalt(II) Tropocoronand Complexes

  摘要：

  A series of Co(II) complexes of the tropocoronand ligand system [TC-n,m](2-) (n,m = 3,3; 3,4; 4,4; 4,5; 5,5; 6,6; 7,7)have been prepared and fully characterized. X-ray structural analyses have been carried out on [Co(TC-3,3)], [Co(TC-4,4)], [Co(TC-4,5)], [Co(TC-5,5)], [Co(TC-6,6)], and the dinuclear complex [Co-2(mu-OAc)(mu-OH)(TC-7,7)]. In the mononuclear series, the coordination geometries vary from square-planar for [Co(TC-3,3)] to tetrahedral for [Co(TC-6,6)]. The twist angle, defined as the dihedral angle between the two five-membered aminotroponiminate chelate rings, increases from 9.0 to 84.5 degrees as a result of increasing torsional strain within the polymethylene linker chains of the tropocoronand macrocycle. The change in geometry from square-planar to tetrahedral, accompanied by a change in spin state from S = 1/2 to S = 3/2, occurs abruptly between [Co(TC-4,4)] and [Co(TC-4,5)] as determined by X-ray crystallographic and solid state magnetic studies. This dependence of geometry and spin state on ligand size is similar to that observed previously in the Ni(II) system, where the low spin to high spin transformation occurred at the [Ni(TC-4,5)]/[Ni(TC-5,5)] junction. The shift in the position of this transformation with metal ion is an indication of the greater preference of Co(n) for tetrahedral geometry compared with Ni(II). The dinuclear [Co-2(mu-OAc)(mu-OH)(TC-7,7)] compound was prepared from Co(OAc)(2) . 4H(2)O and H-2(TC-7,7) in refluxing MeOH. The complex contains two Co(II) atoms sitting in the plane of the macrocycle, bridged by an acetate group on one side of the ligand plane and a hydroxo group on the other. All of the complexes are air sensitive in solution to varying degree but stable in the solid state. Crystallographic data: [Co(TC-3,3)], monoclinic, P2(1), a = 10.187(4) Angstrom, b = 8.466(1) Angstrom, c = 10.227(1) Angstrom, beta = 97.80(3)degrees, Z = 2, R = 0.067, R(W) = 0.068; [Co(TC-4,4)], monoclinic, P2(1)/c, a = 11.109(3) Angstrom, b = 8.561(1) Angstrom, c = 20.088(6) Angstrom, beta = 90.53(2)degrees, Z = 4, R = 0.039, R(W) = 0.042; [Co(TC-4,5)], monoclinic, P2/c, a = 22.041(3) Angstrom, b = 9.351(2) Angstrom, c = 19.859(3) Angstrom, beta = 106.43(1)degrees, Z = 8, R = 0.048, R(W) = 0.054; [Co(TC-5,5)], hexagonal, P6(1)22, a = 10.965(2) Angstrom, c = 30.692(5) Angstrom, Z = 6, R = 0.038, R(W) = 0.048; [Co(TC-6,6)], orthorhombic, P2(1)2(1)2(1), a = 10.644(2) Angstrom, b = 11.426(2) Angstrom, c = 19.083(2) Angstrom, Z = 4, R = 0.047, R(W) = 0.051; [Co-2(mu-OAc)(mu-OH)(TC-7,7)]. Et(2)O, orthorhombic, Pbcn, a = 12.298(5) Angstrom, b = 16.128(4) Angstrom, c = 17.252(7) Angstrom, Z = 4, R = 0.036, R(W) = 0.042.

  DOI：

  10.1021/ic00127a010

文献信息

• Influence of Tetraazamacrocyclic Ligands on the Nitric Oxide Reactivity of their Cobalt(II) Complexes
  作者：Julia Kozhukh、Stephen J. Lippard

  DOI：10.1021/ja305011g

  日期：2012.7.11

  oxide (NO) were investigated. When [Co(TC-5,5)] was allowed to react with NO(g), the CoNO}(8) mononitrosyl [Co(NO)(TC-5,5)] was isolated and structurally characterized. In contrast, a Co(NO)(2)}(10) species formed when [Co(TC-6,6)] was exposed to NO(g), and the nitrito [Co(NO(2))(TC-6,6)] complex was structurally and spectroscopically characterized from the reaction mixture. The Co(NO)(2)}(10) species

  研究了四氮杂大环 tropocoronand (TC) 配体的钴 (II) 配合物与一氧化氮 (NO) 的反应。当 [Co(TC-5,5)] 与 NO(g) 反应时，CoNO}(8) 单亚硝基 [Co(NO)(TC-5,5)] 被分离出来并进行结构表征。相比之下，当 [Co(TC-6,6)] 暴露于 NO(g) 和亚硝基 [Co(NO(2))(TC -6,6)] 复合物从反应混合物中进行结构和光谱表征。Co(NO)(2)}(10) 物种被指定为双（二亚硝基钴）配合物 [Co(2)(NO)(4)(TC-6,6)] 通过光谱比较与独立合成和特征材料。这些结果为原冠和环尺寸对钴 (II) 配合物的一氧化氮反应性的影响提供了第一个证据。