Fe^IV(5,10,15-tris(pentafluorophenyl)corrole)Cl | 226922-75-4

• 英文名称: Fe^IV(5,10,15-tris(pentafluorophenyl)corrole)Cl
• 英文别名: 5,10,15-tris(pentafluorophenyl)corrole iron(IV) chloride；5,10,15-tri(pentafluorophenyl)corrolatoiron chloride；meso-tris(pentafluorophenyl)corrolatoiron(IV)chloride；(tpfc)FeCl；Fe(5,10,15-tris(pentafluorophenyl)corrole(3-))Cl；[Fe(5,10,15-tris(pentafluorophenyl)corrolato)Cl]；chloro(tri(pentafluorophenyl)corrolato)iron(IV)；ClFe(5,10,15-tris(pentafluorophenyl)corrole)；[Fe(tpfc)Cl]；FeCl(TF5PC)
• CAS: 226922-75-4
• 化学式: C₃₇H₈ClF₁₅FeN₄
• 分子量: 884.773
• InChiKey: DOZOTSWNJBZVNU-XDBICYDFSA-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：

  Fe^IV(5,10,15-tris(pentafluorophenyl)corrole)Cl 在 三乙胺 作用下， 以 乙腈 为溶剂， 生成 (5,10,15-tris(pentafluorophenyl)corrolato)iron(III)
  参考文献：
  名称：

  Reduction of Cobalt and Iron Corroles and Catalyzed Reduction of CO₂

  摘要：

  The role of cobalt and iron corroles in catalytic CO2 reduction has been studied. Chemical, electrochemical, and photochemical reductions of the stable metal corroles Ph3PCoIII(tpfc) (tpfc = 5,10,15-tris(pentafluorophenyl)corrole), ClFeIV(tpfc), and CIFeIV(tdcc) (tdcc = 5,10,15-tris(2,6-dichlorophenyl)corrole) have been carried out in acetonitrile solutions. Stepwise reduction to the [M-II(tpfc)](-) and [M-1(tpfc)](2-) states was observed in all cases. Gradual reduction with sodium amalgam permitted recording of the optical absorption spectra of the various oxidation states and showed that the M-1 state reacts with CO2. Cyclic voltammetry in Ar-saturated acetonitrile solutions permitted determination of the following half-wave potentials: for Ph3PCOIII (tpfc), 1.11 V, 0.72 V, -0.42 V (E-pc), - 1.44 V, -2.3 V (E-pc); for ClFeIV(tpfc), 0.44 V, - 1.01 V (E-pc), - 1.60 V, -2.2 V (E-pc); for ClFeIV(tdcc), 0.24 V, - 1.18 V (E-pc), - 1.78 V vs SCE with a scan rate of 0. 1 V s(-1). Cyclic voltammetry in CO2-saturated solutions indicated that the Co-1 and Fe-1 complexes react with CO2 and that the reduced Fe(tdcc) complex is the most efficient electrocatalyst for CO2 reduction, showing the largest catalytic currents among these corroles. Photochemical reduction in CO2-saturated acetonitrile solutions containing p-terphenyl (TP) as a sensitizer and triethylamine (TEA) as a reductant led to production of CO and H, These experiments also show that Fe(tdcc) is more effective than the other corroles as a CO2 reduction catalyst. The present finding that the M-1 oxidation states of the cobalt and iron corroles can react with CO2 is in contrast with the case of the respective porphyrins and phthalocyanines, which do not react with CO2 until they are reduced beyond the M-1 state.

  DOI：

  10.1021/jp013668o
• 作为产物：
  描述：

  iron(II) chloride tetrahydrate 、 5,10,15-tris(pentafluorophenyl)corrole 以 N,N-二甲基甲酰胺 为溶剂， 反应 1.5h， 以80%的产率得到Fe^IV(5,10,15-tris(pentafluorophenyl)corrole)Cl
  参考文献：
  名称：

  重氮铁乙酸乙酯催化铁（IV）-Corrole催化醛的立体选择

  摘要：

  首先研究了铁（IV）-络合物作为在三苯基膦存在下醛与重氮乙酸乙酯进行烯化反应的催化剂。观察到具有高反选择性的芳族醛的高效烯化反应，表明铁甲氧烷是一种新型的有希望的烯化反应催化剂。事实证明，铁（IV）甲氧磷将膦嗪转化为叶立德是本系统中的关键步骤。

  DOI：

  10.1021/acs.organomet.5b00069
• 作为试剂：
  描述：

  4-甲基环己酮 在 Fe^IV(5,10,15-tris(pentafluorophenyl)corrole)Cl 、 氧气 、 苯甲醛 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 6.0h， 以50.5%的产率得到5-methyloxepan-2-one
  参考文献：
  名称：

  金属 Corroles 催化的好氧 Baeyer-Villiger 氧化

  摘要：

  环己酮向ε-己内酯的转化是通过金属corrole催化的B-V氧化反应实现的。发现铁堇Fe(tpfc)Cl对B-V氧化表现出最好的催化活性，并且该活性可以通过4 A-MS添加剂进一步增强。

  DOI：

  10.1002/ejoc.202200462

文献信息

• Photochemical Generation of a Highly Reactive Iron−Oxo Intermediate. A True Iron(V)−Oxo Species?
  作者：Dilusha N. Harischandra、Rui Zhang、Martin Newcomb

  DOI：10.1021/ja0542439

  日期：2005.10.1

  agent in a preparative reaction with cis-cyclooctene. Representative rate constants for oxidation reactions by the new transient at ambient temperature were k = 5900 M-1 s-1 for cyclooctene and k = 570 M-1 s-1 for ethylbenzene. The new transient is more than 6 orders of magnitude more reactive with typical organic reductants than expected for an iron(IV)-oxo corrole radical cation and 100 times more

  由相应的氯化物制备的 5,10,15-三（五氟苯基）氯酸铁（IV）或硝酸盐的激光闪光光解产生了高反应性的铁-氧瞬态，被鉴定为铁（V）-氧类物质基于其紫外可见光谱和高反应性以及类比相关锰物种的光化学配体裂解反应。在与顺式环辛烯的制备反应中，瞬态被证明是氧代转移剂。在环境温度下新瞬态氧化反应的代表性速率常数是 k = 5900 M-1 s-1 环辛烯和 k = 570 M-1 s-1 乙苯。新的瞬态与典型有机还原剂的反应性比铁 (IV)-氧代科尔罗自由基阳离子的反应性高 6 个数量级以上，比类似的带正电荷的铁 (IV)-氧代卟啉自由基阳离子的反应性高 100 倍。配体铁 (V)-氧代物质缓慢电子转移异构化为铁 (IV)-氧代配体自由基阳离子在实验室和自然界中卟啉-铁催化剂的反应中可能很重要。
• Hangman effect on hydrogen peroxide dismutation by Fe(iii) corroles
  作者：Daniel J. Graham、Dilek K. Dogutan、Matthias Schwalbe、Daniel G. Nocera

  DOI：10.1039/c2cc30580a

  日期：——

  Hangman Fe(III) corroles catalyse H2O2 disproportionation at a faster rate and display a more pronounced hangman effect than their one electron oxidized analogues owing to their ability to bypass high energy intermediates by redox-leveling derived from the use of the corrole as a non-innocent ligand.

  Hangman Fe(III) corroles催化H2O2的非均匀反应速度更快，并表现出比其单电子氧化类似物更明显的吊人效应，这归因于它们能够通过将corrole用作非无辜配体所产生的红氧平衡来绕过高能中间体。
• A comparative study of electrocatalytic hydrogen evolution by iron complexes of corrole and porphyrin from acetic acid and water
  作者：Ya-Qian Zhong、Md. Sahadat Hossain、Ying Chen、Qi-Hang Fan、Shu-Zhong Zhan、Hai-Yang Liu

  DOI：10.1007/s11243-019-00307-5

  日期：2019.8

  evolution of hydrogen. In neutral buffer solution, evolution of hydrogen turnover frequency (TOF) values for iron corrole and iron porphyrin were 274 and 233 h−1 at an overpotential of 838 mV versus standard hydrogen electrode (SHE). The corresponding TOF values had dropped sharply to 19.79 h−1 and 14.36 h−1 in acetic acid media at an overpotential of 942 mV versus SHE. Interestingly, hydrogen evolution

  带有吸电子中观-C6F5 基团的corrole 和卟啉的铁配合物已被用于电催化析氢。在中性缓冲溶液中，与标准氢电极 (SHE) 相比，在 838 mV 的过电位下，铁钴和铁卟啉的氢转换频率 (TOF) 值的演变分别为 274 和 233 h-1。在乙酸介质中，相对于 SHE 的过电位为 942 mV，相应的 TOF 值急剧下降至 19.79 h-1 和 14.36 h-1。有趣的是，由 Fe(III) 卟啉催化的析氢主要是通过 Fe(I)-H 中间体，而对于 Fe(IV) corole 观察到更高价的 Fe(III)-H 中间体。
• Iron complexes of tris(4-nitrophenyl)corrole, with emphasis on the (nitrosyl)iron complex
  作者：Pinky Singh、Irena Saltsman、Atif Mahammed、Israel Goldberg、Boris Tumanskii、Zeev Gross

  DOI：10.1142/s1088424612500605

  日期：2012.5

  The iron complexes of 5,10,15-tris(4-nitrophenyl)corrole have been prepared and characterized by various spectroscopic techniques. The (nitrosyl)iron complex is diamagnetic and its X-ray structure reveals an almost perfectly linear Fe–N–O bond. EPR spectroscopy in conjunction with ¹⁵N labelling were used to deduce the redox centre of the one-electron reduction and oxidation products of the (nitrosyl)iron corrole.

  我们制备了 5,10,15-三(4-硝基苯基)烯丙基醚的铁络合物，并利用各种光谱技术对其进行了表征。(亚硝基)铁络合物具有二磁性，其 X 射线结构显示出几乎完美的线性 Fe-N-O 键。利用 EPR 光谱和 15N 标记推断出了（亚硝基）铁珊瑚的单电子还原和氧化产物的氧化还原中心。
• Copolymerization of Epoxides with Carbon Dioxide Catalyzed by Iron–Corrole Complexes: Synthesis of a Crystalline Copolymer
  作者：Koji Nakano、Kazuki Kobayashi、Takahiro Ohkawara、Hideyuki Imoto、Kyoko Nozaki

  DOI：10.1021/ja4028633

  日期：2013.6.12

  Iron-corrole complexes were found to copolymerize epoxides with CO2. The first iron-catalyzed propylene oxide/CO2 copolymerization has been accomplished. Moreover, the glycidyl phenyl ether (GPE)/CO2 copolymerization with this catalyst provided a crystalline material as a result of the isotactic poly(GPE) moiety.