3-nitro-5,10,15-tris[(4-tert-butylphenyl)corrolato]silver(III) | 1000041-30-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 蒽
• 英文名称: 3-nitro-5,10,15-tris[(4-tert-butylphenyl)corrolato]silver(III)
• CAS: 1000041-30-4
• 化学式: C₄₉H₄₆AgN₅O₂
• 分子量: 844.805
• InChiKey: NXHITXWTLWYTAE-HUTBPLKVSA-N

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：
  None
• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为产物：
  描述：

  silver(I) nitrite 、 5,11,16-tris-(4-tert-butylphenyl)corrole 在 iodine 作用下， 以 乙腈 为溶剂， 生成 3-nitro-5,10,15-tris[(4-tert-butylphenyl)corrolato]silver(III)
  参考文献：
  名称：

  Functionalization of Corroles:  The Nitration Reaction

  摘要：

  The reaction of meso-triarylcorroles with AgNO2 proceeds with concomitant metalation and peripheral substitution to give the corresponding nitro-substituted silverIII corrole complex. The substitution is highly regioselective, giving only the corresponding 3-nitro derivative, among the different possible isomers. The results obtained indicate that the reaction intermediate is the pi-cation radical of the complex, which is then attacked by nitrite ion. This was proven by the reaction of the copper corrole complexes with NaNO2: in this case, the nitration reaction proceeded without the addition of an oxidant, because of the pi-cation radical character of the copper complex. The reaction is also successful in the case of 2,3,17,18-tetraethyl-8,12-diacetoxymethyl-7,13-dimethylcorrole (AMCorH3), with the formation of the meso-substituted silver corrole derivative (NO2)3AMCorAg (fully characterized by X-ray crystallography), the first of its kind to be reported. Two of the corroles are characterized by cyclic voltammetry and spectroelectrochemistry in dichloromethane, and the site of electron transfer is elucidated.

  DOI：

  10.1021/ic7014572

文献信息

• Demetalation of Silver(III) Corrolates
  作者：Manuela Stefanelli、Jing Shen、Weihua Zhu、Marco Mastroianni、Federica Mandoj、Sara Nardis、Zhongping Ou、Karl M. Kadish、Frank R. Fronczek、Kevin M. Smith、Roberto Paolesse

  DOI：10.1021/ic900859a

  日期：2009.7.20

  corroles although longer reaction times were necessary in this case. To study in greater detail the corrole demetalation behavior, selected Ag(III) derivatives were characterized by cyclic voltammetry in pyridine, and the demetalation products spectrally characterized after controlled potential reduction in a thin-layer spectroelectrochemical cell.

  已经测试了银(III) 腐蚀物脱金属的几种程序。酸性条件诱导银离子的去除，但它们也可以促进伴随的咔咯核氧化成异咔咯物质，其程度将取决于特定的酸性介质。通过添加肼不能完全避免这种氧化，特别是在3-NO 2取代的络合物的情况下，其在除去银离子后定量地转化为相应的3-NO 2 ,5-羟基异咔啉。分离了几种 β-硝基异咔啉产物，并对其中一种进行了结构表征。然后测试了银(III)corrolates脱金属的电化学和化学还原方法，目的是避免异corroles的形成。虽然与硼氢化钠的反应被证明对于使未取代的银咯咯盐脱金属非常有效，但对于 β-硝基衍生物来说情况并非如此，其中外围硝基被硼氢化物还原，得到相应的 3-氨基游离碱咯咯物质。对于β-硝基咔咯银配合物，使用DBU/THF溶液获得了成功的方法，该方法以良好的产率提供了作为单一反应产物的3-NO 2咔咯游离碱化合物。这些条件对于未取代的咔咯也有效，尽管