(5,10,15-tris(pentafluorophenyl)corrolato)iron(III) | 431892-25-0

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: (5,10,15-tris(pentafluorophenyl)corrolato)iron(III)
• 英文别名: [Fe(III)(5,10,15-tris(pentafluorophenyl)corrolate)]；[Fe(meso-tris(pentafluorophenyl)corrolato)]；Fe(5,10,15-tris(pentafluorophenyl)corrole)；[Fe(F15-TPC)]
• CAS: 431892-25-0
• 化学式: C₃₇H₈F₁₅FeN₄
• 分子量: 849.32
• InChiKey: MISVDIBAOOLXMM-GRFMCKRTSA-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：

  盐酸 、 (5,10,15-tris(pentafluorophenyl)corrolato)iron(III) 在 air 作用下， 以 not given 为溶剂， 生成 Fe^IV(5,10,15-tris(pentafluorophenyl)corrole)Cl
  参考文献：
  名称：

  高反应性氧化铁中间体的光化学生成。真正的铁 (V)−Oxo 物种？

  摘要：

  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。

  DOI：

  10.1021/ja0542439
• 作为产物：
  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
• 作为试剂：
  描述：

  三乙胺 在 (5,10,15-tris(pentafluorophenyl)corrolato)iron(III) 对三联苯 作用下， 以 乙腈 为溶剂， 生成 氢气
  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

文献信息

• Substituent Effects on Nitrosyl Iron Corrole Complexes Fe(Ar₃C)(NO)
  作者：Crisjoe A. Joseph、Matthew S. Lee、Alexei V. Iretskii、Guang Wu、Peter C. Ford

  DOI：10.1021/ic051956j

  日期：2006.3.1

  Ford, P. C. J. Am. Chem. Soc. 2005, 127, 6737-6743), the second-order rate constants, k(NO), are all much faster ((1-9) x 10(8) M(-1) s(-1) at 298 K) than those for analogous iron(III) complexes of porphyrins. However, on a more microscopic level there is no obvious pattern in these rates with respect to the donor properties of the aryl ring substituents. The high reactivity of the ferric triarylcorrolates

  制备了一系列铁（III）Fe（Ar3C）（NO）在芳基上具有不同取代基的亚硝酰基三（5,10,15-芳基）-corrolate配合物，并比较了某些光谱和反应性能。各种Fe（Ar3C）（NO）配合物的循环伏安分析表明，相对于取代基的电子给体性质，单电子氧化电位和单电子还原电位均以系统且几乎相同的趋势响应。在亚硝酰基拉伸频率nu（NO）中观察到了类似的模式，该频率随较强的供体取代基而适度降低。Fe（Ar3C）（NO）溶液在甲苯中的快速光解会导致NO解离，然后迅速形成[瞬态]依赖的瞬态衰减（大概是Fe（Ar3C））以再生原始光谱。如在较早的对Fe（TNPC）（NO）（TNPC3- = 5,10,15-三（4-硝基-苯基）Corcorate）的快速光解研究中所见，Joseph，C.; Ford，PCJ Am.Chem.Soc （2005，127，6737-6743），二阶速率常数k（NO）在298
• Production of a Putative Iron(V)−Oxocorrole Species by Photo-Disproportionation of a Bis-Corrole−Diiron(IV)−μ-Oxo Dimer: Implication for a Green Oxidation Catalyst
  作者：Dilusha N. Harischandra、Gerald Lowery、Rui Zhang、Martin Newcomb

  DOI：10.1021/ol900480p

  日期：2009.5.21

  Photodisproportionation of a bis-corrole-diiron(IV)-mu-oxo dimer gave a corrole-iron(ill) species and a corrole-iron(V)-oxo species that can be detected and studied in real time. Air oxidation of the corrole-iron(ill) species regenerated the bis-corrole-diiron(IV)-mu-oxo dimer, allowing the development of a photocatalytic method for organic oxidations using molecular oxygen and visible light.