5-(tert-butoxycarbonylazo)-10,20-diphenylporphyrinatonickel(II) | 876863-25-1

• 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)-10,20-diphenylporphyrinatonickel(II)
• CAS: 876863-25-1
• 化学式: C₃₇H₂₈N₆NiO₂
• 分子量: 647.358
• InChiKey: VWMOONPXAAHRFG-KRNCZASPSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  肼基甲酸叔丁酯 、 5-(tert-butoxycarbonylazo)-10,20-diphenylporphyrinatonickel(II) 在 palladium diacetate 、 R-(+)-1,1'-联萘-2,2'-双二苯膦 作用下， 反应 336.0h， 以47%的产率得到5,15-[N,N'-bis(tert-butoxycarbonylamino)]diimino-10,20-diphenylporphodimethenatonickel(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：

  [10-bromo-5,15-diphenylporphyrinato]-magnesium(II) 在 palladium diacetate 、 caesium carbonate 、 R-(+)-1,1'-联萘-2,2'-双二苯膦 作用下， 以 四氢呋喃 为溶剂， 反应 14.5h， 生成 5-(tert-butoxycarbonylazo)-10,20-diphenylporphyrinatonickel(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

文献信息

• Modified porphyrinoids from carbazates and hydrazones and the first crystal structure of a di-iminoporphodimethene
  作者：Louisa J. Esdaile、John C. McMurtrie、Peter Turner、Dennis P. Arnold

  DOI：10.1016/j.tetlet.2005.08.004

  日期：2005.10

  Novel porphyrinoids with interrupted conjugation (di-iminoporphodimetlienes) result from the Pd-catalyzed coupling of meso-bromo porphyrins and their metal complexes with carbazates and hydrazones, followed by aerial oxidation. X-ray crystallography revealed a saddle shape for molecules of the nickel(II) complex of a di-iminoporphodimethene. (c) 2005 Elsevier Ltd. All rights reserved.