5,10,15-tris(pentafluorophenyl)corrole cobalt(III) triphenyl phosphine | 226922-76-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 三苯基化合物
• 英文名称: 5,10,15-tris(pentafluorophenyl)corrole cobalt(III) triphenyl phosphine
• 英文别名: 5,10,15-tris-pentafluorophenylcorrolato-cobalt(III) triphenylphosphine；5,10,15-tris(pentafluorophenyl)cobalt(III) corrole；(tpfc)Co-PPh3；meso-5,10,15-tris(pentafluorophenyl)corrole Co(III)-PPh₃；(C6H5)3PCo(5,10,15-tris(pentafluorophenyl)corrole)；[Co(tpfc)PPh3]
• CAS: 226922-76-5
• 化学式: C₅₅H₂₃CoF₁₅N₄P
• 分子量: 1114.76
• InChiKey: IHBNEVGWMXVTFV-XDBICYDFSA-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：
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• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  5,10,15-tris(pentafluorophenyl)corrole cobalt(III) triphenyl phosphine 、 三乙胺 在 对三联苯 作用下， 以 乙腈 为溶剂， 生成 (C2H5)2NCHCH3Co(5,10,15-tris(pentafluorophenyl)corrole)
  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：

  Co(tpfc)(pyridine)₂ 、 三苯基膦 以 二氯甲烷 为溶剂， 生成 5,10,15-tris(pentafluorophenyl)corrole cobalt(III) triphenyl phosphine
  参考文献：
  名称：

  第9族金属茂的结构和反应模式

  摘要：

  第9组金属茂物1-M（PPh 3）和1-M（py）2 [ M = Co（III），Rh（III），Ir（III）; 1表示5,10,15-三-五氟苯基Corrole的三价阴离子]已经通过结构，光谱和电化学方法充分表征。晶体结构分析表明，双吡啶金属（III）配合物的平均金属-N（吡咯）键长从Co（1.886Å）增至Rh（1.957Å）/ Ir（1.963Å）。金属-N（吡啶）的平均键长也从Co（1.995Å）增加到Rh（2.065Å）/ Ir（2.059Å）。1-M（PPh 3）轴向配位点的配体亲和力以1-Co（PPh 3）的顺序急剧增加）<1-Rh（PPh 3）<1-Ir（PPh 3）。在五坐标和六坐标corrole级数之间，甚至在它们之间，M（+ / 0）还原势均具有令人惊讶的不变性；在相同条件下，CH 2 Cl 2溶液中1-M（PPh 3）的平均M（+ / 0）电势为0.78 V vs

  DOI：

  10.1021/ic901164r
• 作为试剂：
  描述：

  1-癸炔 在 5,10,15-tris(pentafluorophenyl)corrole cobalt(III) triphenyl phosphine 、 硫酸 、 水 作用下， 以 甲醇 为溶剂， 反应 156.0h， 以90%的产率得到2-癸酮
  参考文献：
  名称：

  钴配合物催化的末端炔水合反应。

  摘要：

  首先将钴（III）溶液用于末端炔烃的水合。炔烃水合以良好的产率至优异的产率进行，钴负载量为0.03至0.3mol％。可以耐受多种底物。特别地，该反应在克规模的实验中可以得到90％的产率。

  DOI：

  10.1016/j.tetlet.2020.152426

文献信息

• Selective Substitution of Corroles:  Nitration, Hydroformylation, and Chlorosulfonation
  作者：Irena Saltsman、Atif Mahammed、Israel Goldberg、Elena Tkachenko、Mark Botoshansky、Zeev Gross

  DOI：10.1021/ja025851g

  日期：2002.6.1

  work demonstrates the feasibility and power of electrophilic substitution on the peripheral carbon atoms of triarylcorroles as a synthetic tool to new derivatives. The large difference in the reactivity of the various carbon atoms on the macrocycle was shown to be of electronic rather than steric origin. A careful choice of reagents and a delicate control of reaction conditions allowed the selective

  这项工作证明了在三芳基可罗的外围碳原子上亲电取代作为合成新衍生物的工具的可行性和能力。大环上各种碳原子反应性的巨大差异被证明是电子的而不是空间的。仔细选择试剂和精细控制反应条件允许选择性合成新衍生物，在所有这些衍生物中，仅在大环的直接连接的吡咯环中选择性地发生取代。这已通过各种产品的 X 射线晶体学及其核磁共振谱的详细分析得到证实。
• Electrocatalytic Hydrogen Evolution of Cobalt and Free‐base Triaryl Corrole Bearing Hydroxyethyl Amino Groups
  作者：Ying Chen、Qi‐Hang Fan、Md Sahadat Hossain、Shu‐Zhong Zhan、Hai‐Yang Liu、Li‐Ping Si

  DOI：10.1002/ejic.201900996

  日期：2020.2.7

  Four free‐base corroles (F15C, F12C, F10C, F8C) and their cobalt(III) complexes were used as homogeneous electrocatalysts for hydrogen evolution using acetic acid, trifluoroacetic acid and water as proton sources. Free‐base corrole was firstly reported as electrocatalyst for H2 evolution. The results showed that free‐base corrole was active in electrocatalytic hydrogen evolution reaction (HER) in trifluoroacetic

  使用乙酸，三氟乙酸和水作为质子源，使用了四种游离碱腐蚀剂（F 15 C，F 12 C，F 10 C，F 8 C）及其钴（III）络合物作为均相电催化剂来析氢。最早报道了游离碱甲氧作为H 2析出的电催化剂。结果表明，游离碱甲氧在三氟乙酸中的电催化制氢反应（HER）中具有活性。带有羟乙基氨基的钴（III）酯在HER中比其基准酯更有效。四种被测钴（III）的催化活性物种为Co II‐H在乙酸/二甲基甲酰胺溶剂中。在水溶液中，Co III -H和Co II -H都可能参与HER。有趣的是，当使用三氟乙酸作为质子源时，Co II- H分别是F 15 CCo和F 10 CCo的主要活性中间体，以及Co III- H分别是F 12 CCo和F 8 CCo的活性中间体。对于游离碱甲氧基，（· Cor）H 4和[（· Cor）H 3 ] –是催化活性物质。
• Simkhovich, Liliya; Galili, Nitsa; Saltsman, Irena, Inorganic Chemistry, 2000, vol. 39, p. 2703 - 2705
  作者：Simkhovich, Liliya、Galili, Nitsa、Saltsman, Irena、Goldberg, Israel、Gross, Zeev

  DOI：——

  日期：——