(2,3-(NO2)2-5,10,15-tritolylcorrole)CoPPh3 | 1376758-63-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2,3-(NO2)2-5,10,15-tritolylcorrole)CoPPh3
• 英文别名: 2,3-(NO2)2TTCorrCoPPh3
• CAS: 1376758-63-2
• 化学式: C₅₈H₄₂CoN₆O₄P
• 分子量: 976.976
• InChiKey: SPPMYSJCNJIICW-YGUZVCDXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 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

• 作为产物：
  描述：

  5,10,15-tris(4-methylphenyl)corrole 在 silver(I) nitrite 、 sodium nitrite 作用下， 以 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 1.5h， 生成 (2,3-(NO2)2-5,10,15-tritolylcorrole)CoPPh3
  参考文献：
  名称：

  β-Nitro-5,10,15-tritolylcorroles

  摘要：

  Functionalization of the beta-pyrrolic positions of the corrole macrocycle with -NO2 groups is limited at present to metallocorrolates due to the instability exhibited by corrole free bases under oxidizing conditions. A careful choice of the oxidant can limit the transformation of corroles into decomposition products or isocorrole species, preserving the corrole aromaticity, and thus allowing the insertion of nitro groups onto the corrole framework. Here we report results obtained by reacting 5,10,15-tritolylcorrole (TTCorrH(3)) with the AgNO2/NaNO2 system, to give mono- and dinitrocorrole derivatives when stoichiometry is carefully controlled. Reactions were found to be regioselective, affording the 3-NO(2)TTCorrH(3) and 3,17-(NO2)(2)TTCorrH(3) isomers as the main products in the case of mono- and disubstitution, in 53 and 20% yields, respectively. In both cases, traces of other mono- and disubstituted isomers were detected, which were structurally characterized by X-ray crystallography. The influence of the beta-nitro substituents on the corrole properties is studied in detail by UV-visible, electrochemical, and spectroelectrochemical characterization of these functionalized corroles. Density functional theory (DFT) and time-dependent DFT (TDDFT) calculations of the ground and excited state properties of these beta-nitrocorrole derivatives also afforded significant information, closely matching the experimental observations. It is found that the beta-NO2 substituents conjugate with the pi-aromatic system of the macrocycle, which initiates significant changes in both the spectroscopic and redox properties of the so functionalized corroles. This effect is more pronounced when the nitro group is introduced at the 2-position, because in this case the conjugation is, for steric reasons, more efficient than in the 3-nitro isomer.

  DOI：

  10.1021/ic3007926