chloroiron 5,10,15-tris(4-methylphenyl)corrolate | 388075-98-7

• 英文名称: chloroiron 5,10,15-tris(4-methylphenyl)corrolate
• 英文别名: (meso-tris(p-tolyl)corrolato)iron(IV) chloride；(5,10,15-tris(4-methylphenyl)corrolate)FeCl；ttcorrFeCl；FeCl(TTC)
• CAS: 388075-98-7
• 化学式: C₄₀H₂₉ClFeN₄
• 分子量: 656.997
• InChiKey: WMWFETMSGDBSGY-SATREPFYSA-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：

  chloroiron 5,10,15-tris(4-methylphenyl)corrolate 、 苯基溴化镁 以 乙醚 、 二氯甲烷 为溶剂， 反应 0.17h， 以70%的产率得到
  参考文献：
  名称：

  Phenyl Derivative of Iron 5,10,15-Tritolylcorrole

  摘要：

  The phenyl iron complex of 5,10,15-tritolylcorrole was prepared by reaction of the starting chloro iron complex with phenylmagnesium bromide in dichloromethane. The organometallic complex was fully characterized by a combination of spectroscopic methods, X-ray crystallography, and density functional theory (DFT) calculations. All of these techniques support the description of the electronic structure of this phenyl iron derivative as a low-spin iron(IV) coordinated to a closed-shell corrolate trianion and to a phenyl monoanion. Complete assignments of the H-1 and C-13 NMR spectra of the phenyl iron derivative and the starting chloro iron complex were performed on the basis of the NMR spectra of the regioselectively beta-substituted bromo derivatives and the DFT calculations.

  DOI：

  10.1021/ic5003572
• 作为产物：
  描述：

  iron(II) chloride 、 5,10,15-tris(p-methylphenyl)corrole 以 N,N-二甲基甲酰胺 为溶剂， 生成 chloroiron 5,10,15-tris(4-methylphenyl)corrolate
  参考文献：
  名称：

  β-Nitro Derivatives of Iron Corrolates

  摘要：

  Two different methods for the regioselective nitration of different meso-triarylcorroles leading to the corresponding beta-substituted nitrocorrole iron complexes have been developed. A two-step procedure affords three Fe(III) nitrosyl products-the unsubstituted corrole, the 3-nitrocorrole, and the 3,17-dinitrocorrole. In contrast, a one-pot synthetic approach drives the reaction almost exclusively to formation of the iron nitrosyl 3,17-dinitrocorrole. Electron-releasing substituents on the meso-aryl groups of the triarylcorroles induce higher yields and longer reaction times than what is observed for the synthesis of similar triarylcorroles with electron-withdrawing functionalities, and these results can be confidently attributed to the facile formation and stabilization of an intermediate iron corrole pi-cation radical. Electron-withdrawing substituents on the meso-aryl groups of triarylcorrole also seem to labilize the axial nitrosyl group which, in the case of the pentafluorophenylcorrole derivative, results in the direct formation of a disubstituted iron mu-oxo dimer complex. The influence of meso-aryl substituents on the progress and products of the nitration reaction was investigated. In addition, to elucidate the most important factors which influence the redox reactivity of these different iron nitrosyl complexes, selected compounds were examined by cyclic voltammetry and thin-layer UV-visible or FTIR spectroelectrochemistry in CH2Cl2.

  DOI：

  10.1021/ic3002459

文献信息

• Electrochemical and Electronic Absorption Spectroscopic Studies of Substituent Effects in Iron(IV) and Manganese(IV) Corroles. Do the Compounds Feature High-Valent Metal Centers or Noninnocent Corrole Ligands? Implications for Peroxidase Compound I and II Intermediates
  作者：Erik Steene、Tebikie Wondimagegn、Abhik Ghosh

  DOI：10.1021/jp012037r

  日期：2001.11.1

  We report here an electrochemical and optical spectroscopic study of new Fe(IV) and Mn(IV) meso-triarylcorrole complexes. The complexes studied are three Fe(IV)Cl, three Mn(IV)Cl, and three dimeric Fe(IV)OFe(IV) meso-tris(p-X-phenyl)corrole complexes, where X = CH3, H, and CF3. The first oxidation potentials of the Fe(IV)Cl and Mn(IV)Cl corrole complexes are considerably higher than those of the corresponding

  我们在此报告新的 Fe(IV) 和 Mn(IV) 内消旋三芳基考罗配合物的电化学和光学光谱研究。研究的配合物是三个 Fe(IV)Cl、三个 Mn(IV)Cl 和三个二聚 Fe(IV)OFe(IV) 内消旋三(pX-苯基)corrole 配合物，其中 X = CH3、H 和 CF3。Fe(IV)Cl 和 Mn(IV)Cl corrole 配合物的第一氧化电位明显高于相应的 Fe(IV) corrole μ-oxo 二聚体，表明氯化物配合物中的 corrole 配体已经被氧化成一个激进的状态。这与 Walker 及其同事（参考文献 12）的建议一致，即（八烷基corrolato）FeIVCl 配合物中的铁中心最好描述为中间自旋（S = 3/2），并且它反铁磁耦合到 corrole π -激进的。我们试图通过 DFT 计算阐明这种反铁磁耦合的性质，并提出它是由金属（dz2）-corrole（“b
• Nitration of iron corrolates: further evidence for non-innocence of the corrole ligand
  作者：Manuela Stefanelli、Sara Nardis、Luca Tortora、Frank R. Fronczek、Kevin M. Smith、Silvia Licoccia、Roberto Paolesse

  DOI：10.1039/c0cc05491g

  日期：——

  Mono- and di-substituted β-nitro derivatives have been obtained from the reaction of ttcorrFeCl with sodium nitrite in refluxing DMF. This result is unprecedented for iron corrolates and further evidences the non-innocent character of the corrole ligand.

  在回流的 DMF 中，ttcorrFeCl 与亚硝酸钠反应得到了单取代和二取代的 β-硝基衍生物。这一结果在铁珊瑚酸盐中是前所未有的，进一步证明了珊瑚配体的非无辜性。
• Electronic Configurations and the Effect of Peripheral Substituents of (Nitrosyl)iron Corroles
  作者：Wanjie Ren、Charles E. Schulz、Mark H. Shroyer、Wei Xu、Shibo Xi、Pengfei An、Wenping Guo、Jianfeng Li

  DOI：10.1021/acs.inorgchem.2c03026

  日期：2022.12.19

  have been isolated and investigated by various techniques including single-crystal X-ray diffraction, UV–vis spectroscopy, cyclic voltammetry, Fourier transform infrared, NMR, and absorption fine structure spectroscopy. Multitemperature and high-magnetic-field (3, 6, and 9 T) Mössbauer spectroscopy was also applied on all three complexes, which determined the S = 0 diamagnetic states, consistent with

  几十年来，关于（亚硝基）咯咯铁的电子构型一直存在争论。在这项工作中，具有不同对位取代苯基（TPC、TTC 和T p FC = 三（苯基、4-甲苯基或 4-氟苯基）咔咯，分别）已通过各种技术分离和研究，包括单晶 X 射线衍射、紫外-可见光谱、循环伏安法、傅里叶变换红外、核磁共振和吸收精细结构光谱。多温度和高磁场（3、6 和 9 T）穆斯堡尔光谱也应用于所有三个配合物，这确定了S= 0 抗磁状态，与磁化率和电子顺磁共振测量一致。比较了不同泛函的密度泛函理论预测，新的计算策略与实验穆斯堡尔参数（Δ E Q和 δ）显着一致，允许进一步分配 FeNO} 6 –（corrole 3– ）的电子配置) 与反铁磁耦合 ( S = 1 / 2 , Fe III ) 和 ( S = 1 / 2 , NO)。para的电子捐赠/取款能力之间的相关序列还建立了取代基和还原/氧化电位、金属面外位移（Δ 4和 Δ 23）和穆斯堡尔参数（V