ferric meso-tetra(4-sulfonatophenyl)porphine | 60489-11-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: ferric meso-tetra(4-sulfonatophenyl)porphine
• 英文别名: tetra(4-sulfonatophenyl)porphine；Fe(III) tetrakis(4-sulfonatophenyl)porphyrin；iron(III) tetrasulfophenylporphyrin；{Fe(III)(tetrakis(4-sulfonatophenyl)porphyrin)}(3-)；5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrinatoiron(III)；meso-tetra(4-sulfonatophenyl)porphyrinato)iron(III)；tetrakis(4-sulfonatophenyl)porphyrinato iron(III)；tetra(p-sulfonatophenyl)porphyrinatoiron(III)；iron(III)-tetrakis(sulfonatophenyl)porphyrin；[Fe(5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin)](3-)；iron(III)(meso-(tetra-p-sulfonatophenyl)porphyrin)；iron(III)-tetra(p-sulfophenyl)porphine；Fe(III)-TPPS
• CAS: 60489-11-4
• 化学式: C₄₄H₂₄FeN₄O₁₂S₄
• 分子量: 984.805
• InChiKey: ZETLZMJYAVSGMY-DAJBKUBHSA-J

计算性质

• 辛醇/水分配系数(LogP)：
  3.18
• 重原子数：
  65.0
• 可旋转键数：
  8.0
• 环数：
  10.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  263.38
• 氢给体数：
  0.0
• 氢受体数：
  16.0

反应信息

• 作为反应物：
  描述：

  ferric meso-tetra(4-sulfonatophenyl)porphine 在 氧化亚氮 作用下， 以 水 为溶剂， 25.0 ℃ 、100.0 kPa 条件下， 生成
  参考文献：
  名称：

  A Dissociative Mechanism for Reactions of Nitric Oxide with Water Soluble Iron(III) Porphyrins

  摘要：

  DOI：

  10.1021/ja972448e
• 作为产物：
  描述：

  以 水 为溶剂， 25.0 ℃ 、100.0 kPa 条件下， 生成 ferric meso-tetra(4-sulfonatophenyl)porphine
  参考文献：
  名称：

  A Dissociative Mechanism for Reactions of Nitric Oxide with Water Soluble Iron(III) Porphyrins

  摘要：

  DOI：

  10.1021/ja972448e

文献信息

• Water-Soluble Nitroxyl Porphyrin Complexes Fe^IITPPSHNO and Fe^IITPPSNO^– Obtained from Isolated Fe^IITPPSNO^•
  作者：Agostina Mazzeo、Juan Pellegrino、Fabio Doctorovich

  DOI：10.1021/jacs.9b09161

  日期：2019.11.20

  The first biomimetic water soluble FeII-porphyrin nitroxyl complexes were obtained and characterized by UV-Vis in protonated and deprotonated forms by reduction of previously isolated and characterized FeIITPPSNO•. The pKa involved in the FeII-HNO ⇄ FeII-NO- + H+ equilibrium was estimated to be around 9.7. The FeIITPPSHNO complex spontaneously reoxidizes to the nitrosyl form following a first order

  获得了第一个仿生水溶性 FeII-卟啉硝酰基复合物，并通过紫外-可见光以质子化和去质子化形式通过还原先前分离和表征的 FeIITPPSNO• 进行表征。FeII-HNO ⇄ FeII-NO- + H+ 平衡中涉及的 pKa 估计约为 9.7。FeIITPPSHNO 复合物在一级动力学衰减后自发地再氧化为亚硝酰基形式，测得的动力学常数为 k = 0.017 s-1。实验表明，HNO 加合物经历了 H-NO 键的单分子均裂裂解。DFT 计算表明该反应存在根皮素自由基中间体。去质子化的 NO-复合物更稳定，半衰期约为 10 分钟。
• Mechanisms of Ferriheme Reduction by Nitric Oxide:  Nitrite and General Base Catalysis¹
  作者：Bernadette O. Fernandez、Ivan M. Lorkovic、Peter C. Ford

  DOI：10.1021/ic049532x

  日期：2004.8.1

  ferriheme model Fe(III)(TPPS) (TPPS = tetra(4-sulfonatophenyl)porphyrinato) has been investigated in moderately acidic solution. In the absence of added or adventitious nitrite, this reaction displays general base catalysis with several buffers in aqueous solutions. It was also found that the nitrite ion, NO(2)(-), is a catalyst for this reaction. Similar nitrite catalysis was demonstrated for another ferriheme

  亚铁血红素模型Fe（III）的还原性亚硝基化（Fe（III）（P）+ 2NO + H（2）O = Fe（II）（P）（NO）+ NO（2）（-）+ 2H（+）） III）（TPPS）（TPPS =四（4-磺酰基苯基）卟啉酮）已在中等酸性溶液中进行了研究。在不存在亚硝酸盐或不添加亚硝酸盐的情况下，该反应在水溶液中使用几种缓冲液显示出一般的碱催化作用。还发现亚硝酸根离子NO（2）（-）是该反应的催化剂。另一个亚铁血红素模型系统Fe（III）（TMPy）（TMPy = meso-tetrakis（N-methyl-4-pyridyl）porphyrinato）以及亚铁血红素蛋白met-hemoglobin（metHb）和met-yoyoglobin（ metMb）在缓冲水溶液中。因此，看来这种催化是还原性亚硝基化产物的一般机理。提出了两种亚硝酸盐催化机理。首先，将NO（2）（-）可视为通过亲核加
• Structural and electrochemical characterization of metallo-porphyrins intercalated into ZnCr-layered double hydroxides: some evidence of dimer formation
  作者：Christine Taviot-Guého、Matilte Halma、Khaled Charradi、Claude Forano、Christine Mousty

  DOI：10.1039/c1nj20400a

  日期：——

  In this study, inorganic–organic hybrids were prepared by intercalation of metal complexes (Zn and Fe) of 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (TSPP) into Zn2Cr layered double hydroxides (LDH) by coprecipitation method at constant pH. The resulting materials were characterized by powder X-ray diffraction, UV-Vis and FTIR spectroscopies showing the intercalation of porphyrins between the ZnCr layers. While monomer species are intercalated in the case of Zn2Cr-ZnTSPP, the intercalation of dimers is likely to occur in the case of Zn2Cr-FeTSPP. In both materials, a perpendicular orientation of the porphyrin ring against the hydroxide layers is proposed. Of particular interest is the good stability of ZnCr-LDH host over a wide pH range. The electrochemical behavior of these hybrid materials in both neutral (pH 7.0) and acid media (pH 4.5) was investigated by cyclic voltammetry. Zn2Cr-FeTSPP exhibits an electrocatalytic activity for the reduction of oxygen, hydrogen peroxide and nitrite.

  在这项研究中，通过共沉淀法将5,10,15,20-四(4-磺基苯基)卟啉(TSPP)的金属配合物(Zn和Fe)嵌入Zn2Cr层状双氢氧化物(LDH)中制备了无机-有机杂化物。在恒定的pH值下。通过粉末 X 射线衍射、紫外-可见光和 FTIR 光谱对所得材料进行了表征，显示了 ZnCr 层之间嵌入了卟啉。虽然在 Zn2Cr-ZnTSPP 中插入单体，但在 Zn2Cr-FeTSPP 中可能发生二聚体插入。在这两种材料中，提出了卟啉环相对于氢氧化物层的垂直取向。特别令人感兴趣的是 ZnCr-LDH 主体在较宽的 pH 范围内具有良好的稳定性。通过循环伏安法研究了这些杂化材料在中性（pH 7.0）和酸性介质（pH 4.5）中的电化学行为。 Zn2Cr-FeTSPP 具有还原氧气、过氧化氢和亚硝酸盐的电催化活性。
• Resonance Raman investigation of pH-dependent equilibria of water-soluble iron porphyrins
  作者：Steven E. J. Bell、Ronald E. Hester、Jeremy N. Hill、David R. Shawcross、John R. Lindsay Smith

  DOI：10.1039/ft9908604017

  日期：——

  Resonance Raman spectroscopy has been used to probe the structures of; tetrakis(1-methylpyridinium-4-yl)porphinatoiron(III), FeIII(T4MPyP); tetrakis(1-methylpyridium-2-yl)porphinatoiron(III), FeIII(T2MPyP); tetrakis(4-sulphonatophenyl)porphinatoiron(III), FeIII(TSPP); and tetrakis(4-carboxylatophenyl)porphinatoiron(III), FeIII(TCPP), over a wide pH range. The anionic complexes FeIII(TSPP) and FeIII(TCPP) contain high-spin iron(III) at all pHs. Both these complexes exhibit marked spectral changes at ca. pH 6 which correspond to conversion from the diaquo species, in acid solution, to hydroxy-or µ-oxo dimer, transitions at ca. pH 6. However, at pH > 11.5 for FeIII(T4MPyP) and pH > 9 for FeIII(T2MPyP) a second equilibrium process is observed, leading to two new species. One of these is readily assigned as the low-spin iron(III) dihydroxy complex by analogy with spectra of the dicyano complex. The second species is assigned to the hydroxy iron(II) complex by comparison with photochemically generated FeII(T4MPyP)(OH). The formation of iron(II) species in alkaline solutions of FeIII(T4MPyP) and FeIII(T2MPyP) is entirely unexpected and the significance of the observation to previous investigations of the pH-dependent behaviour of these complexes is discussed.

  共振拉曼光谱被用来探测以下物质的结构：四(1-甲基吡啶-4-基)卟吩铁(III)，FeIII(T4MPyP)；四(1-甲基吡啶-2-基)卟吩铁(III)，FeIII(T2MPyP)；四(4-磺酸基苯基)卟吩铁(III)，FeIII(TSPP)；以及四(4-羧酸基苯基)卟吩铁(III)，FeIII(TCPP)。阴离子络合物 FeIII(TSPP) 和 FeIII(TCPP) 在所有 pH 值下都含有高自旋铁(III)。这两种络合物在 pH 值约为 6 时都表现出明显的光谱变化，这与在酸性溶液中从二钴物种转化为羟基或 µ-oxo 二聚体（在 pH 值约为 6 时发生转变）相对应。 然而，当 FeIII(T4MPyP) 的 pH 值大于 11.5 和 FeIII(T2MPyP) 的 pH 值大于 9 时，会观察到第二个平衡过程，从而产生两种新物种。通过与二氰基络合物的光谱进行类比，其中一种很容易被归类为低自旋铁（III）二羟基络合物。通过与光化学生成的 FeII(T4MPyP)(OH) 进行比较，第二个物种被归类为羟基铁（II）络合物。在 FeIII(T4MPyP) 和 FeIII(T2MPyP) 的碱性溶液中形成铁(II)物种是完全出乎意料的。
• A Diatomic Molecule Receptor That Removes CO in a Living Organism
  作者：Hiroaki Kitagishi、Shigeru Negi、Akiko Kiriyama、Akino Honbo、Yukio Sugiura、Akira T. Kawaguchi、Koji Kano

  DOI：10.1002/anie.200906149

  日期：——

  A CO stripper: The O2‐bound form of an iron(II) porphyrin cyclodextrin supramolecular complex (hemoCD) infused into a rat vein reacted with internal CO through ligand exchange, and the CO‐bound hemoCD was immediately excreted in the urine (see picture). The hemoCD acting as a CO receptor made it possible to quantify endogenous CO in a living organism.

  CO汽提塔：注入大鼠静脉的铁（II）卟啉环糊精超分子复合物（hemoCD）的O 2结合形式通过配体交换与内部CO反应，CO结合的血CD立即从尿液中排泄（参见图片）。充当CO受体的bloodCD使定量活生物体中的内源性CO成为可能。