5,10,15-tris[(4-methylphenyl)corrolato]copper(III) | 444987-86-4

• 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: 5,10,15-tris[(4-methylphenyl)corrolato]copper(III)
• 英文别名: [meso-tri-p-tolylcorrolato]copper(III)；(5,10,15-tritolyl-isocorrolato)Cu；(TTCor)Cu；[5,10,15-tritolylcorrole]Cu
• CAS: 444987-86-4
• 化学式: C₄₀H₂₉CuN₄
• 分子量: 629.243
• InChiKey: MCFNBCXNWXGDEI-BZLUFMOKSA-N

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：

  5,10,15-tris[(4-methylphenyl)corrolato]copper(III) 在 溴 、 吡啶 作用下， 以 氯仿 为溶剂， 反应 2.0h， 生成 copper β-octabromo-meso-tris(p-Me-phenyl)corrole
  参考文献：
  名称：

  改进的β-八溴-内消旋-三芳基甲酚衍生物的合成

  摘要：

  尽管作为各种金属茂衍生物的起始原料有大量应用，但仍然认为游离碱β-八溴-内消旋-三芳基Corroles难以获得。原因从繁琐的柱色谱纯化需求到所选系统的还原性脱金属方案的局限性不等。在这里，我们报告说，对于许多β-八溴-内消旋-tris（p -X-苯基）甲酚衍生物，可以完全避免使用柱色谱法，其中X = CF 3，NO 2，F，H，CH 3和OCH 3; 相反，可以通过从氯仿/甲醇中重结晶获得分析纯的产物。此外，我们已经通过相应的Mn（III）的还原脱金属反应，提出了一种迄今为止无法获得的，位阻受阻的配体β-八溴-内消旋-三（2,6-二氯苯基）甲酸酯H 3 [Br 8 TDCPC]的优化合成方法。） 复杂的。与我们的较早的报告β-八溴-内消旋-三（五氟苯基）corrole，H 3 [BR 8 TPFPC]，一套完整的优化的合成协议从而代替一个良好的数目的β -octabromo-内消旋-三芳基

  DOI：

  10.1016/j.jinorgbio.2015.07.017
• 作为产物：
  描述：

  copper(II) acetate monohydrate 、 5,10,15-tris(4-methylphenyl)corrole 在 吡啶 作用下， 反应 0.25h， 生成 5,10,15-tris[(4-methylphenyl)corrolato]copper(III)
  参考文献：
  名称：

  改进的β-八溴-内消旋-三芳基甲酚衍生物的合成

  摘要：

  尽管作为各种金属茂衍生物的起始原料有大量应用，但仍然认为游离碱β-八溴-内消旋-三芳基Corroles难以获得。原因从繁琐的柱色谱纯化需求到所选系统的还原性脱金属方案的局限性不等。在这里，我们报告说，对于许多β-八溴-内消旋-tris（p -X-苯基）甲酚衍生物，可以完全避免使用柱色谱法，其中X = CF 3，NO 2，F，H，CH 3和OCH 3; 相反，可以通过从氯仿/甲醇中重结晶获得分析纯的产物。此外，我们已经通过相应的Mn（III）的还原脱金属反应，提出了一种迄今为止无法获得的，位阻受阻的配体β-八溴-内消旋-三（2,6-二氯苯基）甲酸酯H 3 [Br 8 TDCPC]的优化合成方法。） 复杂的。与我们的较早的报告β-八溴-内消旋-三（五氟苯基）corrole，H 3 [BR 8 TPFPC]，一套完整的优化的合成协议从而代替一个良好的数目的β -octabromo-内消旋-三芳基

  DOI：

  10.1016/j.jinorgbio.2015.07.017

文献信息

• Electronic Absorption, Resonance Raman, and Electrochemical Studies of Planar and Saddled Copper(III) <i>meso</i>-Triarylcorroles. Highly Substituent-Sensitive Soret Bands as a Distinctive Feature of High-Valent Transition Metal Corroles
  作者：Ingar H. Wasbotten、Tebikie Wondimagegn、Abhik Ghosh

  DOI：10.1021/ja0113697

  日期：2002.7.1

  We present here a first systematic study of substituent effects in metallocorroles, based on electronic absorption, resonance Raman (RR), and infrared (IR) spectroscopic studies and electrochemical measurements on 10 copper(III) meso-triarylcorroles, Cu(III)[beta-Y(8)TArC], where the beta-substituent Y = H or Br and the meso-aryl group Ar = C(6)F(5) or p-X-C(6)H(4) and X = CF(3), H, CH(3), and OCH(3)

  基于电子吸收、共振拉曼 (RR) 和红外 (IR) 光谱研究以及对 10 种铜 (III) 内消旋三芳基可咯、Cu(III) β 的电化学测量，我们在此首次系统地研究了金属可咯中的取代基效应。 -Y(8)TArC]，其中 β 取代基 Y = H 或 Br，内消旋芳基 Ar = C(6)F(5) 或 pXC(6)H(4) 且 X = CF(3) 、H、CH(3) 和 OCH(3)。结果提供了许多重要的见解。(1) RR（和 IR）结果表明，在 1400-1550 cm(-1) 区域中至少有两个甚至可能更多的高频段在 β-八溴化反应中表现出显着的频率降移，因此符合结构敏感的要求标记带。DFT 几何优化表明，对于所研究的 β-八溴-内消旋-三芳基可罗衍生物而言，鞍状构象显然是首选，并且 β-八溴化导致可罗大环的许多骨架键距离扩大，与观察到的频率下降一致。(2) 平面 Cu(III)[TArC]
• Effect of NO₂ substitution and solvent on UV-visible spectra, redox potentials and electron transfer mechanisms of copper β-nitrotriarylcorroles. Proposed electrogeneration of a Cu(I) oxidation state
  作者：Lina Ye、Zhongping Ou、Yuanyuan Fang、Yang Song、Bihong Li、Rui Liu、Karl M. Kadish

  DOI：10.1142/s1088424616500899

  日期：2016.7

  examined doubly reduced nitrocorroles in DMF and pyridine, suggesting formation of a Cu(I) species with an unreduced macrocycle which is represented as Cu[Formula: see text]-Cor[Formula: see text]. Changes in redox potentials and absorption spectra of the nitrocorroles are examined as a function of solvent and substituents on the meso-phenyl rings of the compounds and comparisons are made between spectral

  合成了三种含有[分子式：见正文]-吡咯硝基取代基的三芳基铜铜，并对其在非水介质中的光谱和电化学性质进行了表征。检查的化合物表示为[公式：见正文]-NO2(YPh)3CorCu，其中 Cor 是三苯基莠的三阴离子，Y 是 Cl、H 或 CH3该化合物的三个内消旋苯环的对位上的取代基。来自吸收光谱、电化学和薄层光谱电化学的数据与 CH 中 Cu[公式：见正文]-Cor[公式：见正文]的初始分配一致2氯2, DMF 和吡啶，并在这些溶剂中第一次单电子还原后，生成具有未还原大环的形式 Cu(II) corrole，表示为 Cu[公式：见正文]-Cor[公式：见正文]。双重还原的[公式：见正文]-硝基克罗在 CH 中在 439 nm 处有一个尖锐的 Soret 带，在 611 nm 处有一个明确的 Q 带2氯2. 对于在 DMF 和吡啶中检测到的三种双还原硝基克咯，可以看到类似的吸收光谱，这表明形成了具有未还原大环的
• Moving corrole towards a red-record: synthesis of β-acrolein Ga and Cu corroles using the Vilsmeier reaction
  作者：A. Savoldelli、S. Nardis、D. Genovese、L. Prodi、F. R. Fronczek、K. M. Smith、R. Paolesse

  DOI：10.1039/c7nj04705c

  日期：——

  Copper and gallium β-acrolein corroles have been obtained by reaction of corrole complexes with 3-(dimethylamino)-acrolein/phosphoryl chloride (3-DMA/POCl3) under Vilsmeier conditions. In the case of the Ga complex, up to four acroleyl substituents have been introduced at the β-peripheral positions of the corrole macrocycle. The introduction of the acroleyl moiety on the corrole scaffold strongly influences

  在Vilsmeier条件下，通过使所述配合物与3-（二甲氨基）-丙烯醛/磷酰氯（3-DMA / POCl 3）反应，可获得铜和镓的β-丙烯醛腐蚀。在Ga络合物的情况下，已在Corrole大环的β周围位置引入了多达四个丙烯醛取代基。丙烯醛部分在冠状支架上的引入强烈影响了Ga冠状分子的光物理行为。
• Synthesis and Characterization of Free-Base, Copper, and Nickel Isocorroles
  作者：Giuseppe Pomarico、Xiao Xiao、Sara Nardis、Roberto Paolesse、Frank R. Fronczek、Kevin M. Smith、Yuanyuan Fang、Zhongping Ou、Karl M. Kadish

  DOI：10.1021/ic100730j

  日期：2010.6.21

  A series of free-base and metalated isocorroles represented as (TT-n-iso-Cor)H-2 and (TT-n-iso-Cor)M-II, where n=5 or 10 and M = Ni or Cu, were synthesized and characterized by electrochemistry and spectroelectrochemistry in CH2Cl2 containing 0.1 M tetra-n-butylammonium perchlorate. The metalation of the free-base macrocydes with Co-II, Mn-IIII, or Zn-II was also attempted but was unsuccessful. Six isocorroles were isolated and shown to undergo two stepwise oxidations to give pi-cation radicals and dications in CH2Cl2, with the most stable products being obtained in the case of the 10-substituted derivatives. The same isocorroles could also be reduced by one or two electrons, but the initial one-electron addition products are unstable and undergo a rapid chemical reaction giving a reduced corrole or corrole-like product, which could be reoxidized to the corresponding (TTCor)M at a controlled positive potential. This series of reactions effectively illustrates an isocorrole to corrole conversion upon reduction and reoxidation and was monitored by both electrochemistry and thin-layer spectroelectrochemistry.
• Functionalization of Corroles:  The Nitration Reaction
  作者：Manuela Stefanelli、Marco Mastroianni、Sara Nardis、Silvia Licoccia、Frank R. Fronczek、Kevin M. Smith、Weihua Zhu、Zhongping Ou、Karl M. Kadish、Roberto Paolesse

  DOI：10.1021/ic7014572

  日期：2007.12.1

  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.