| 184099-36-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• CAS: 184099-36-3
• 化学式: C₂₁H₂₀CoN₅O₃
• 分子量: 449.415
• InChiKey: AMPAHMKVNAGXEO-UHFFFAOYSA-K

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：

  叔丁基过氧化氢 、 以 二氯甲烷 为溶剂， 以85%的产率得到
  参考文献：
  名称：

  钴 (III)-烷基过氧配合物的合成、结构和反应性及其在碳氢化合物的化学计量和催化氧化中的作用

  摘要：

  尽管 Co(III)-烷基过氧物种经常被认为是用钴催化剂对烃类进行工业氧化的中间体，但离散 [LCoIII-OOR] 配合物的例子及其氧化能力的研究很少。在这项工作中，已经合成了 12 种具有两种不同配体 L 和各种一级、二级和三级 R 基团的此类配合物，其中 7 种已通过 X 射线晶体学表征。两个配体 N,N-bis[2-(2-pyridyl)ethyl]pyridine-2,6-dicarboxamide (Py3PH2, 1) 和 N,N-bis[2-(1-pyrazolyl) 的二价阴离子 (L2-) )乙基]吡啶-2,6-二甲酰胺 (PyPz2PH2, 2) 除了三个吡啶或一个吡啶和两个吡唑氮外，还以五齿方式与两个去质子化的羧酰胺氮结合 Co(III) 中心，以提供 [LCoIII(H2O)] 和 [LCoIII(OH)] 类型的复合物。[LCoIII(OH)] 复合物与 ROOH

  DOI：

  10.1021/ja9814873
• 作为产物：
  描述：

  在 LiOH*H₂O 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 以35.8%的产率得到
  参考文献：
  名称：

  Synthesis, Properties, and Structure of a Stable Cobalt(III) Alkyl Peroxide Complex and Its Role in the Oxidation of Cyclohexane

  摘要：

  Three cobalt(II) complexes of Py(3)PH(2) (H's are the dissociable amide H's), a strong-field ligand with two peptide groups, have been synthesized. They are [Co(Py(3)P)(H2O)]ClO4 . H2O (6), [Co(Py(3)P)(OH)] (7), and [Co(Py(3)P)(OO(t)Bu)].2CH2Cl2 (8). Complex 6 crystallizes in the monoclinic space group C2 with a = 22.695(6) Angstrom, b = 10.284(2) Angstrom, c = 10.908(3) Angstrom, alpha = 90 degrees, beta = 112.17(2)degrees, gamma = 90 degrees, V = 2357.7(10) Angstrom(3) and Z = 4. Its structure has been refined to R = 3.91% on the basis of 1844 I > 2 sigma(I) data. Complex 8 crystallizes in the monoclinic space group P2(1)/n with a = 16.720(4) Angstrom, b = 10.641(3) Angstrom, c = 16.776(3) Angstrom, alpha = 90 degrees, beta = 99.76(2)degrees, gamma = 90 degrees, V = 2941.5(12) Angstrom(3), and Z = 4. The structure of 8 has been refined to R = 6.37% on the basis of 4776 I > 2 sigma(I) reflections. In all three complexes, the doubly deprotonated Py(3)P(2-) ligand binds the cobalt(III) center in a pentadentate fashion with five nitrogens situated in two deprotonated amido groups and three pyridine rings. The aqua complex 6 can easily be converted into the hydroxo complex 7 by the addition of 1 equiv of base. The transformation 6 <-> 7 is reversible, and the pK(a) of the coordinated water molecule in 6 is 7. Complex 8 is the first example of a structurally characterized Co(III) alkyl peroxide complex that contains two deprotonated amido groups bonded to the metal center. Like a few alkyl peroxide complexes of tervalent cobalt, 8 oxidizes alkanes upon thermal decomposition. When cyclohexane is used as the substrate, cyclohexanol, cyclohexanone, and cyclohexyl chloride are the products. Complex 7 is the intermediate in the formation of 8 and is also the thermal decomposition product of 8. In single turnover oxidation of cyclohexane by 8 at the optimum temperature of 80 degrees C, a maximum yield of 59% of the oxidized products is obtained. The mechanism of cyclohexane oxidation by 8 involves exclusive homolytic scission of the O-O bond in 8. The (t)BuO(.) radicals generated in such a process abstract an ii atom from cyclohexane to afford cyclohexyl radicals, which in turn react with dioxygen and produce cyclohexanol and cyclohexanone presumably via a Russell-type termination reaction. The oxidation of cyclohexane by 8 can be either stoichiometric or catalytic. In the presence of excess TBHP, 8 affords more oxidized products, indicating multiple turnovers.

  DOI：

  10.1021/ic960500m