5-(tert-butoxycarbonylazo)-10,15,20-triphenylporphyrinatonickel(II) | 1539299-46-1

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: 5-(tert-butoxycarbonylazo)-10,15,20-triphenylporphyrinatonickel(II)
• CAS: 1539299-46-1
• 化学式: C₄₃H₃₂N₆NiO₂
• 分子量: 723.456
• InChiKey: AGUGFIYCMROSML-FTUVJPMQSA-M

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：

  5-(tert-butoxycarbonylazo)-10,15,20-triphenylporphyrinatonickel(II) 在 sodium tetrahydroborate 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 0.67h， 生成 5-[(ethoxycarbonyl)hydrazo]-10,15,20-triphenylporphyrinatonickel(II)
  参考文献：
  名称：

  Facile dearomatisation of porphyrins using palladium-catalysed hydrazination: the 5,15-diiminoporphodimethenes and their redox products

  摘要：

  The synthesis, electronic absorption and H-1 NMR spectra of a suite of novel porphyrinoids derived from meso-bromoporphyrins by palladium-catalysed aminations using ethyl and tert-butylcarbazates are reported. Instead of the expected carbazate-substituted porphyrins, a facile oxidative dearomatisation of the porphyrin ring occurs in high yield, especially for the nickel(II) complexes, resulting in high yields of 5,15-diiminoporphodimethenes (DIPDs). The analogous zinc(II) and free base DIPDs were also charactedsed, the former by X-ray crystallography. The oxidation and reduction reactions of DIPDs and their precursor carbazate porphyrins were studied. Density Functional Theory (DFT) was used to calculate the optimised geometries and frontier molecular orbitals of DIPD Ni8c and bis(azocarboxylate) 19c, and Time Dependent DFT calculations allowed the prediction of electronic absorption spectra, whose characteristics corresponded well with those of the observed solution spectra. In the latter case, the calculated low-energy absorptions were unlike those of a typical porphyrin, due to the near-degeneracy of the highest filled frontier orbitals, and the wide energy separation between the unfilled orbitals. This feature was present in the observed spectrum. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2013.11.006
• 作为产物：
  描述：

  5-[(ethoxycarbonyl)hydrazo]-10,15,20-triphenylporphyrinatonickel(II) 在 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以95%的产率得到5-(tert-butoxycarbonylazo)-10,15,20-triphenylporphyrinatonickel(II)
  参考文献：
  名称：

  Facile dearomatisation of porphyrins using palladium-catalysed hydrazination: the 5,15-diiminoporphodimethenes and their redox products

  摘要：

  The synthesis, electronic absorption and H-1 NMR spectra of a suite of novel porphyrinoids derived from meso-bromoporphyrins by palladium-catalysed aminations using ethyl and tert-butylcarbazates are reported. Instead of the expected carbazate-substituted porphyrins, a facile oxidative dearomatisation of the porphyrin ring occurs in high yield, especially for the nickel(II) complexes, resulting in high yields of 5,15-diiminoporphodimethenes (DIPDs). The analogous zinc(II) and free base DIPDs were also charactedsed, the former by X-ray crystallography. The oxidation and reduction reactions of DIPDs and their precursor carbazate porphyrins were studied. Density Functional Theory (DFT) was used to calculate the optimised geometries and frontier molecular orbitals of DIPD Ni8c and bis(azocarboxylate) 19c, and Time Dependent DFT calculations allowed the prediction of electronic absorption spectra, whose characteristics corresponded well with those of the observed solution spectra. In the latter case, the calculated low-energy absorptions were unlike those of a typical porphyrin, due to the near-degeneracy of the highest filled frontier orbitals, and the wide energy separation between the unfilled orbitals. This feature was present in the observed spectrum. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2013.11.006