F20TPPFe(III)-OCH3 | 854691-18-2

• 分子结构分类: 有机化合物
• 英文名称: F20TPPFe(III)-OCH3
• 英文别名: iron(III) (methoxy)tetrakis(pentafluorophenyl)porphyrin；iron(III) methoxide tetrakispentafluorophenyl porphyrin；F20TPPFe(III)OMe
• CAS: 854691-18-2
• 化学式: C₄₅H₁₁F₂₀FeN₄O
• 分子量: 1059.42
• InChiKey: DYYWNCCCDSMNQI-VTVSBRCESA-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 、 F20TPPFe(III)-OCH3 以 甲醇 为溶剂， 生成 iron(III) (methanol)tetrakis(pentafluorophenyl)porphyrin
  参考文献：
  名称：

  Effects of Methanol on the Thermodynamics of Iron(III) [Tetrakis(pentafluorophenyl)]porphyrin Chloride Dissociation and the Creation of Catalytically Active Species for the Epoxidation of Cyclooctene

  摘要：

  In a previous study, the authors showed that iron(III) [ tetrakis(pentafluorophenyl)] porphyrin chloride [(F20TPP)FeCl]is catalytically inactive for cyclooctene epoxidation by hydrogen peroxide in acetonitrile but is catalytically active if the solvent contains methanol. It was suggested that the precursor to the active species is (F20TPP)Fe(OCH3) in methanol-containing solvents. The present study was aimed at evaluating this hypothesis. (F20TPP) Fe(OCH3) was synthesized and characterized by H-1 NMR but was found to be inactive in both acetonitrile and methanol. Further investigation of the interactions of (F20TPP) FeCl with methanol in acetonitrile/methanol mixtures was then carried out using NMR. Two species, characterized by H-1 NMR resonances at 82 and 65 ppm, were observed. The first resonance is attributed to the, ss-pyrrole protons on molecularly dissolved (F20TPP) FeCl, whereas the second is attributed to,-pyrrole protons of [(F20TPP) Fe](+) cations that are stabilized by coordination with a molecule of methanol, viz., [(F20TPP) Fe(CH3OH)] +. The relative concentration of [(F20TPP) Fe(CH3OH)](+) increases as the fraction of methanol in the solvent increases, suggesting that methanol facilitates the dissociation of (F20TPP) FeCl into cations and anions. A thermodynamic model of the dissociation is proposed and found to describe successfully the experimental observation over a range of solvent compositions, porphyrin concentrations, and temperatures. UV-visible spectroscopy was also used to validate the developed model. In addition, the observed rate constant for cyclooctene epoxidation was found to be proportional to the concentration of [(F20TPP) Fe(CH3OH)](+) calculated using the thermodynamic model, suggesting that this intermediate is a precursor to the species that catalyzes olefin epoxidation. The catalytic activity of [(F20TPP) Fe(CH3OH)](+) was further confirmed through experiments in which (F20TPP) Fe(OCH3) dissolved in methanol was reacted with HCl(aq). This reaction produced a product with an NMR peak at 65 ppm attributable to [(F20TPP) Fe(CH3OH)](+), and this mixture was found to have activity for cyclooctene epoxidation similar to that of (F20TPP) FeCl dissolved in methanol.

  DOI：

  10.1021/ic0521067
• 作为产物：
  描述：

  (5,10,15,20-tetrakis(pentafluorophenyl)porphyrinato)iron(III) chloride 、 sodium methylate 以 甲醇 、 苯 为溶剂， 以97%的产率得到F20TPPFe(III)-OCH3
  参考文献：
  名称：

  Effects of Methanol on the Thermodynamics of Iron(III) [Tetrakis(pentafluorophenyl)]porphyrin Chloride Dissociation and the Creation of Catalytically Active Species for the Epoxidation of Cyclooctene

  摘要：

  In a previous study, the authors showed that iron(III) [ tetrakis(pentafluorophenyl)] porphyrin chloride [(F20TPP)FeCl]is catalytically inactive for cyclooctene epoxidation by hydrogen peroxide in acetonitrile but is catalytically active if the solvent contains methanol. It was suggested that the precursor to the active species is (F20TPP)Fe(OCH3) in methanol-containing solvents. The present study was aimed at evaluating this hypothesis. (F20TPP) Fe(OCH3) was synthesized and characterized by H-1 NMR but was found to be inactive in both acetonitrile and methanol. Further investigation of the interactions of (F20TPP) FeCl with methanol in acetonitrile/methanol mixtures was then carried out using NMR. Two species, characterized by H-1 NMR resonances at 82 and 65 ppm, were observed. The first resonance is attributed to the, ss-pyrrole protons on molecularly dissolved (F20TPP) FeCl, whereas the second is attributed to,-pyrrole protons of [(F20TPP) Fe](+) cations that are stabilized by coordination with a molecule of methanol, viz., [(F20TPP) Fe(CH3OH)] +. The relative concentration of [(F20TPP) Fe(CH3OH)](+) increases as the fraction of methanol in the solvent increases, suggesting that methanol facilitates the dissociation of (F20TPP) FeCl into cations and anions. A thermodynamic model of the dissociation is proposed and found to describe successfully the experimental observation over a range of solvent compositions, porphyrin concentrations, and temperatures. UV-visible spectroscopy was also used to validate the developed model. In addition, the observed rate constant for cyclooctene epoxidation was found to be proportional to the concentration of [(F20TPP) Fe(CH3OH)](+) calculated using the thermodynamic model, suggesting that this intermediate is a precursor to the species that catalyzes olefin epoxidation. The catalytic activity of [(F20TPP) Fe(CH3OH)](+) was further confirmed through experiments in which (F20TPP) Fe(OCH3) dissolved in methanol was reacted with HCl(aq). This reaction produced a product with an NMR peak at 65 ppm attributable to [(F20TPP) Fe(CH3OH)](+), and this mixture was found to have activity for cyclooctene epoxidation similar to that of (F20TPP) FeCl dissolved in methanol.

  DOI：

  10.1021/ic0521067

文献信息

• A Study of the Mechanism and Kinetics of Cyclooctene Epoxidation Catalyzed by Iron(III) Tetrakispentafluorophenyl Porphyrin
  作者：Ned A. Stephenson、Alexis T. Bell

  DOI：10.1021/ja043380n

  日期：2005.6.1

  conducted of the mechanism and kinetics of cyclooctene epoxidation by hydrogen peroxide catalyzed by iron(III) tetrakispentafluorophenyl [F(20)TPPFe(III)] porphyrin. The formation of cyclooctene oxide, the only product, was determined by gas chromatography, and the consumption of hydrogen peroxide was determined by (1)H NMR. UV-visible spectroscopy was used to identify the state of the porphyrin as a function

  对铁 (III) 四五氟苯基 [F(20)TPPFe(III)] 卟啉催化过氧化氢环辛烯环氧化的机理和动力学进行了研究。环辛烯氧化物的形成是唯一的产物，由气相色谱法确定，过氧化氢的消耗由（1）H NMR 确定。紫外-可见光谱用于确定卟啉的状态作为溶剂组成和反应条件的函数，并跟踪卟啉降解的动力学。发现 F(20)TPPFe(III) 在氯化物连接的形式中是无活性的，但当氯化物配体被甲醇配体取代时变得有活性。F(20)TPPFe(III) 的甲醇连接形式与过氧化氢反应形成铁 (III) 氢过氧化物物质，然后经历异裂和均裂，分别形成铁 (IV) π 自由基阳离子和铁 (IV) 羰基化合物。铁 (IV) π 自由基阳离子负责环辛烯的环氧化，而铁 (IV) 氧代物种负责过氧化氢分解。从所提出的机制发展而来的环辛烯环氧化和过氧化氢分解的动力学准确地描述了实验观察到的动力学。从模型拟合实验数据得出的速率