| 149185-71-7

• 分子结构分类: 有机化合物 - 有机氮化合物
• CAS: 149185-71-7
• 化学式: C₂₀H₂₂CoN₄
• 分子量: 377.415
• InChiKey: PWSOCFMSHWMPJB-WWYMNURWSA-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：

  在 CHCl₃ 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 生成
  参考文献：
  名称：

  Jaynes, B. Scott; Ren, Tong; Liu, Shuncheng, Journal of the American Chemical Society, 1992, vol. 114, p. 9670 - 9671

  摘要：

  DOI：
• 作为产物：
  描述：

  在 (Me₄N)(SC₆F₅) 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成
  参考文献：
  名称：

  五配位硫醇钴（III）和亚硝酰基对苯二酚及其化合物。

  摘要：

  [Co（TC-n，m）] +与（Me4N）（SC6F5）的反应，其中（TC-n，m）是对苯二酚，具有n和m个连接基亚甲基，产生硫醇盐配合物[Co（SC6F5） （TC-3,3）]（1a）和[Co（SC6F5）（TC-4,4）]（2a）进行了结构表征。使用更多的释放电子的硫醇盐得到[Co（TC-n，m）]还原产物和相应的二硫化物。由[Co（TC-n，m）]合成弯曲的亚硝酰基配合物[Co（NO）（TC-3,3）]（1b）和[Co（NO）（TC-4,4）]（2b）。还确定了NO及其结构。化合物1a和1b与所有其他在结构上表征的[MX（TC-3,3）]配合物一样，具有方锥体的几何形状。化合物2a和2b具有三角双锥体的立体化学，以前很少用于Co（III）。尽管1a，1b和2a是顺磁性的，由于金属和NO pi *轨道之间的强抗键pi相互作用，图2b是抗磁性的。在过量的NO存在下，[Co（TC-4,4）

  DOI：

  10.1021/ic010181l

文献信息

• Singlet–Triplet Gaps of Cobalt Nitrosyls: Insights from Tropocoronand Complexes
  作者：Kathrin H. Hopmann、Jeanet Conradie、Espen Tangen、Zachary J. Tonzetich、Stephen J. Lippard、Abhik Ghosh

  DOI：10.1021/acs.inorgchem.5b00901

  日期：2015.8.3

  A density functional theory (DFT) study of CoNO}8 cobalt nitrosyl complexes containing the [n,n]tropocoronand ligand (TC-n,n) has revealed a sharp reduction of singlet–triplet gaps as the structures change from near-square-pyramidal (for n = 3) to trigonal-bipyramidal with an equatorial NO (for n = 5, 6). An experimental reinvestigation of [Co(TC-3,3)(NO)] has confirmed that it is not paramagnetic

  密度泛函理论（DFT）对包含[ n，n ]对苯二酚和配体（TC- n，n）的CoNO} 8钴亚硝酰基复合物的研究表明，随着结构从近乎正方形的变化，单重态-三重态态的间隙急剧减小。 -pyramidal（对于ñ = 3）与赤道NO三角-双锥（对于ñ = 5，6）。对[Co（TC-3,3）（NO）]进行的实验性重新研究证实，它不像最初报道的那样是顺磁性的，而是像所有其他CoNO} 8一样是抗磁性的复合体。此外，DFT计算表明该复合物的单重态-三重态的间隙大约为半eV或更高。在该系列的另一端，预测了[Co（TC-6,6）（NO）]的低能热可及三重态。增强的三重态反应性可能很好地为未能分离出该化合物作为稳定物种提供了部分解释。
• Doerrer, Linda H.; Bautista, Maria T.; Lippard, Stephen J., Inorganic Chemistry, 1997, vol. 36, # 17, p. 3578 - 3579
  作者：Doerrer, Linda H.、Bautista, Maria T.、Lippard, Stephen J.

  DOI：——

  日期：——
• Scott Jaynes; Ren, Tong; Masschelein, Axel, Journal of the American Chemical Society, 1993, vol. 115, # 13, p. 5589 - 5599
  作者：Scott Jaynes、Ren, Tong、Masschelein, Axel、Lippard, Stephen J.

  DOI：——

  日期：——
• Synthesis, Tuning of the Stereochemistry, and Physical Properties of Cobalt(II) Tropocoronand Complexes
  作者：B. Scott Jaynes、Linda H. Doerrer、Shuncheng Liu、Stephen J. Lippard

  DOI：10.1021/ic00127a010

  日期：1995.11

  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.