5,10,15,20-(tetra-2,6-difluorophenyl)porphyrin iron chloride | 221335-24-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并恶唑类
• 英文名称: 5,10,15,20-(tetra-2,6-difluorophenyl)porphyrin iron chloride
• 英文别名: chloro(tetrakis(2,6-difluorophenyl)porphyrinato)iron(III)；(5,10,15,20-tetrakis(2,6-difluorophenyl)porphyrinato)FeCl；tetrakis(2,6-difluororphenyl)porphinatoiron(III) chloride；[meso-5,10,15,20-tetrakis-(2,6-difluorophenyl)porhpyrinato]-iron(III) chloride；5,10,15,20-tetrakis(2,6-difluorophenyl)porphyrin iron(III) chloride；chloro(meso-tetrakis(2,6-difluorophenyl)porphirinato)iron(III)；iron(III) [tetrakis(2,6-difluorophenyl)]porphyrin chloride；iron(III) tetra(2,6-difluorophenyl)porphyrin chloride；[Fe(tetrakis(2,6-difluorophenyl)porphyrinate(2-))Cl]；(meso-tetrakis(2,6-difluorophenyl)porphinato(2-))Fe(III)Cl；(tetrakis(2,6-difluorophenyl)porphyrinate(2-))Fe(III)Cl；[Fe(tetrakis(o-difluorophenyl)porphyrin(2-))Cl]；(2,6-F8TPP)FeCl；F8TPPFe(III)Cl；[FeCl(tetrakis(2,6-difluorophenyl)porphyrinate(2-))]
• CAS: 221335-24-6
• 化学式: C₄₄H₂₀ClF₈FeN₄
• 分子量: 847.957
• InChiKey: KSEKXFHAGYLPEC-TXFZNMFQSA-M

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：
  None
• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  5,10,15,20-(tetra-2,6-difluorophenyl)porphyrin iron chloride 在 HClO₄ 、 H₂O 作用下， 以 二氯甲烷 为溶剂， 以60%的产率得到[Fe(tetrakis(2,6-difluorophenyl)porphyrinate(2-))]2O
  参考文献：
  名称：

  X-ray Structure and Physical Properties of the Oxo-Bridged Complex [(F8-TPP)Fe-O-Cu(TMPA)]+, F8-TPP = Tetrakis(2,6-difluorophenyl)porphyrinate(2-), TMPA = Tris(2-pyridylmethyl)amine: Modeling the Cytochrome c Oxidase Fe-Cu Heterodinuclear Active Site

  摘要：

  The iron/copper heterodinuclear center in cytochrome c oxidases has attracted the interest of inorganic chemists since this is the site of dioxygen (O-2) four-electron four-proton reduction to water by the reduced enzyme, while the oxidized (''resting'') isolated protein dinuclear center exhibits unusual physical, spectroscopic, and ligand-binding properties. We describe here a model compound, [(F-8-TPP)Fe-III-O-Cu-II(TMPA)](+) (3), generated directly from O-2-reduction by 1:1 mixtures of the reduced copper(I) and iron(II) complexes [(TMPA)Cu-I(CH3CN)](+) (1) (TMPA = tris(2-pyridylmethyl)amine) and (F-8-TPP)Fe-II(pip)(2) (2) (F-8-TPP = tetrakis(2,6-difluorophenyl)porpyrinate-(2-), pip = piperidine) in O-2-saturated CH2Cl2 at -80 degrees C; warming to 0 degrees C, followed by precipitation with diethyl ether, affords 3 in similar to 70% yield, An X-ray diffraction study on [(F-8-TPP)Fe-O-Cu(TMPA)](ClO4).3C(7)H(8).2CH(3)CN (3-ClO4) as well as the mu-oxo iron dimer [(F-8-TPP)Fe]O-2.3C(7)H(8) allows for direct structural cc,mparisons, as well as with other relevant compounds. Compound 3 also possesses a linear mu-oxo-bridging ligand, where angle Fe-O-Cu = 178.2-(4)degrees; unusually short metal-oxygen distances of Fe-O = 1.740(5) Angstrom and Cu-O = 1.856(5) Angstrom are observed, and Fe...Cu = 3.596(2) Angstrom. The coordination geometry around Cu is distorted from the usual (i.e., for TMPA-Cu(II) complexes) trigonal-bipyramidal configuration toward a square-based pyramidal arrangement, and the three pyridine rings are situated between the four F-8-TPP phenyl rings, thus leaving one ''slot'' free. H-1-NMR spectra of 3-ClO4 in CD2Cl2 exhibit a pyrrole signal at 65 ppm (corroborated by H-2-NMR) which is upfield shifted relative to ol her axially symmetric high-spin (tetraphenylporphyrinate)iron(III) complexes; this is consistent with electronic/maegnetic coupling of the Fe(III) and Cu(II) centers. Additional upfield-shifted signals are tentatively assigned to the TMPA ligand on copper, thus implicating a bridged structural arrangement which is maintained in solution. A detailed magnetic Mossbauer spectroscopic study (4.2 K at 0, 0.5, and 8 T) has been carried out.The data unambiguously indicate that 3 possesses a high-spin ferric (S-Fe = 5/2) ion and exhibits characteristic parameters: D = 6.0 +/- 0.5 cm(-1) E/D = 0.03 +/- 0.01, Delta E(Q) = -1.26 +/- 0.02 mm/s, eta = 0, delta = 0.46 +/- 0.01 mm/s, and A/g(n) beta(n) = -23.7 +/- 0.3 T. Furthermore, the magnetic properties observed, i.e., in the presence or absence of an applied field, demonstrate that the ferric ion is spin-coupled to the cupric ion to form an overall integer spin system in [(F-8-TPP)(FeO)-O-III-Cu-II(TMPA)](ClO4) (3-ClO4). The Mossbauer isomer shift and quadrupole splitting parameters compare favorably with those previously obtained for data on enzyme resting-state preparations, although they differ in certain details. The conclusion that 3-ClO4 is an S = 2 system is determined by multifield saturation magnetization measurements, carried out both in solution (2-200 K) and the solid state (30-300 K). An exact magnetic coupling constant J (for exchange coupling according to (-2JS(1).S-2)) could not be determined from the solution data, due to the inherent ''noise'' found in these measurements, even for similar to 1 mM solutions. These findings carl into question previous evaluations for the lower limit of \J\ greater than or equal to 200 cm(-1) for the dinuclear Fe(III)-X-Cu(II) site in as-isolated ''resting'' oxidized cytochrome c oxidase enzyme; a lower limit of \J\ greater than 50 cm(-1) is suggested as a better estimate. Solid-state measurements on 3-ClO4 give a value of -J = 87 cm(-1), i.e., moderately strong antiferromagnetic coupling between high-spin iron(III) and copper(II) ions, consistent with the NMR and Mossbauer spectroscopic data. The possible biological relevance of the oxo-bridged complex [(F-8-TPP)Fe-III-O-Cu-II(TMPA)]ClO4) (3-ClO4) and its observed magnetic/electronic properties are discussed.

  DOI：

  10.1021/ja00090a023
• 作为产物：
  描述：

  5,10,15,20-tetrakis(2,6-difluorophenyl)porphyrin 在 iron(III) chloride hexahydrate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 5,10,15,20-(tetra-2,6-difluorophenyl)porphyrin iron chloride
  参考文献：
  名称：

  Preparation of catalysts based on iron(III) porphyrins heterogenized on silica obtained by the Sol-Gel process for hydroxylation and epoxidation reactions

  摘要：

  Solid catalysts have been prepared by chemical interaction of iron(III) porphyrins with the surface of the pores of a silica matrix obtained by the sol-gel method. The presence of the complexes in the silica matrix and the morphology of the obtained particles were studied by UV-Vis spectroscopy, powder X-ray diffractometry, infrared spectroscopy, transmission electron microscopy, electron paramagnetic resonance and thermogravimetric analysis. The catalytic activity of the immobilized iron( III) porphyrins in the oxidation of (Z)-cyclooctene, cyclohexene and cyclohexane was evaluated in dichloromethane/ acetonitrile 1: 1 solvent mixture (v/v) using iodosylbenzene as oxidant. Results were compared with those achieved with the homogeneous counterparts.

  DOI：

  10.1590/s0103-50532010000700020
• 作为试剂：
  描述：

  异丁司特 在 sodium hypochlorite 、 5,10,15,20-(tetra-2,6-difluorophenyl)porphyrin iron chloride 、 十二烷基二甲基苄基氯化铵 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 以65.4%的产率得到2-methyl-1-(10-propan-2-yl-3,6-dioxa-1,11-diazatetracyclo[6.3.0.02,4.05,7]undeca-8,10-dien-9-yl)propan-1-one
  参考文献：
  名称：

  Facile prepartion of unstable metabolic intermediates; Epoxide(s) of pyrazolo[1,5-a]pyridine derivatives by the cytochrome P-450 chemical model.

  摘要：

  通过使用细胞色素P-450的化学模型对生物活性吡唑[1, 5-a]吡啶衍生物进行仿生氧化，得到了相对高产率的6, 7-环氧化物，这些化合物似乎是主要代谢物（即6, 7-二氢-6, 7-二醇）的化学不稳定前体。

  DOI：

  10.1248/cpb.37.1410

文献信息

• Heme/O₂/•NO Nitric Oxide Dioxygenase (NOD) Reactivity: Phenolic Nitration via a Putative Heme-Peroxynitrite Intermediate
  作者：Mark P. Schopfer、Biplab Mondal、Dong-Heon Lee、Amy A. N. Sarjeant、Kenneth D. Karlin

  DOI：10.1021/ja904832j

  日期：2009.8.19

  An oxy-heme complex, the heme-superoxo species (tetrahydrofuran)(F(8))Fe(III)-(O(2)(*-)) (2) (F(8) = an ortho-difluoro substituted tetraarylporphyrinate), reacts with nitrogen monoxide (*NO; nitric oxide) to produce a nitrato-iron(III) compound (F(8))Fe(III)-(NO(3)(-)) (3) (X-ray). The chemistry mimics the action of *NO Dioxygenases (NODs), microbial and mammalian heme proteins which facilitate *NO

  氧-血红素复合物，血红素-超氧物种（四氢呋喃）（F（8））Fe（III）-（O（2）（* -））（2）（F（8）=邻二氟取代的四芳基卟啉酸盐), 与一氧化氮 (*NO; 一氧化氮) 反应生成硝基铁 (III) 化合物 (F(8))Fe(III)-(NO(3)(-)) (3) (X 射线）。化学模拟 *NO 双加氧酶 (NOD)、微生物和哺乳动物血红素蛋白的作用，促进 *NO 解毒/体内平衡。涉及过氧亚硝酸盐中间体复合物；如果在 *NO 与 2 反应之前加入 2,4-二叔丁基苯酚，则会发生邻硝化反应，得到 2,4-二叔丁基-6-硝基苯酚。铁产物是 (F(8))Fe(III)-(OH) (4)。结果表明血红素/O(2)/*NO 化学可能导致过氧亚硝酸盐泄漏和/或外源性底物氧化/硝化反应。
• Insights from kinetic studies of photo-generated compound II models: Reactivity toward aryl sulfides
  作者：Ngo Fung Lee、Dharmesh Patel、Haiyan Liu、Rui Zhang

  DOI：10.1016/j.jinorgbio.2018.03.004

  日期：2018.6

  which are 3 to 4 orders of magnitude greater in comparison to those of alkene epoxidations and activated CH bond oxidations by the same oxo species. Conventional Hammett analyses gave non-linear correlations, indicating no significant charge developed at the sulfur during the oxidation process. For a given substrate, the reactivity order for the iron(IV)-oxo species was 3c < 3b < 3a, which is inverted

  铁（IV）-氧代卟啉[Fe IV（Por）O]（Por = Poprhyrin），通常称为化合物II模型，是通过高度光不稳定的卟啉-铁（III）的可见光照射在三个缺电子配体中产生的溴酸盐或氯酸盐。在CH 3 CN溶液中研究了这些光生[Fe IV（Por）O]（3）与芳基硫与氧转移原子（OAT）反应的动力学。研究中的铁（IV）-氧卟啉包括5,10,15,20-四（2,6-二氯苯基）卟啉-铁（IV）-氧（3a），5,10,15,20-四（2） 1,6-二氟苯基）卟啉-铁（IV）-氧（3b）和5,10,15,20-四（五氟苯基）卟啉-铁（IV）-氧（3c）。不出所料3种有效的氧化剂，可与硫代苯甲醚快速反应，得到相应的亚砜和少量的过氧化砜。在拟一级反应条件下，硫化物氧化反应确定的表观二级速率常数为（9.8±0.1）×10 2 –（3.7±0.3）×10 1  M -1  s -1，为3至4阶。与由
• Reductive Coupling of Nitrogen Monoxide (•NO) Facilitated by Heme/Copper Complexes
  作者：Jun Wang、Mark P. Schopfer、Simona C. Puiu、Amy A. N. Sarjeant、Kenneth D. Karlin

  DOI：10.1021/ic901431r

  日期：2010.2.15

  (TMPA = tris(2-pyridylmethyl)amine). The starting point for heme chemistry is the mononitrosyl complex (F8)Fe(NO) (λmax = 399 (Soret), 541 nm in acetone). Variable-temperature 1H and 2H NMR spectra reveal a broad peak at δ = 6.05 ppm (pyrrole) at room temperature (RT), which gives rise to asymmetrically split pyrrole peaks at 9.12 and 8.54 ppm at −80 °C. A new heme dinitrosyl species, (F8)Fe(NO)2, obtained

  一氧化氮（•NO；一氧化氮）与过渡金属中心的相互作用继续引起人们的极大兴趣，部分原因在于它们在生化过程中的重要性。在这里，我们描述了可能与该过程相关的NO (g)还原偶联化学（即一氧化氮还原酶（NOR）生物化学），它发生在细胞色素c氧化酶（C c Os）的血红素/Cu 活性位点。在本报告中，使用 1:1 比例的血红素和铜络合物组分 (F 8 )Fe (F 8 = 四(2,6-二氟苯基)卟啉 (2-))研究了血红素/Cu/•NO (g)活性) 和 [(TMPA)Cu I (MeCN)] +(TMPA = 三(2-吡啶基甲基)胺)。血红素化学的起点是单亚硝基复合物 (F 8 )Fe(NO)（λ max = 399 (Soret)，丙酮中 541 nm）。变温1 H 和2 H NMR 光谱显示在室温 (RT) 下 δ = 6.05 ppm（吡咯）处有一个宽峰，这会在 -80 °C 下在 9.12
• Spectroscopic Properties and Electronic Structure of Five- and Six-Coordinate Iron(II) Porphyrin NO Complexes:  Effect of the Axial N-Donor Ligand
  作者：V. K. K. Praneeth、Christian Näther、Gerhard Peters、Nicolai Lehnert

  DOI：10.1021/ic050865j

  日期：2006.4.1

  In this paper, the differences in the spectroscopic properties and electronic structures of five- and six-coordinate iron(II) porphyrin NO complexes are explored using [Fe(TPP)(NO)] (1; TPP = tetraphenylporphyrin) and [Fe(TPP)(MI)(NO)] (2; MI = 1-methylimidazole) type systems. Binding of N-donor ligands in axial position trans to NO to five-coordinate complexes of type 1 is investigated using UV-vis

  在本文中，使用[Fe（TPP）（NO）]（1; TPP =四苯基卟啉）和[Fe（ TPP）（MI）（NO）]（2; MI = 1-甲基咪唑）型系统。使用紫外可见吸收和1H NMR光谱研究了N-供体配体在轴向位置上向NO的结合与1型五配位配合物的结合。这样，确定了相应的结合常数Keq，并首次分配了1和2的1H NMR光谱。此外，1 H NMR可以确定碱过量的1溶液中的亚硝基化程度。然后研究了轴向配体对配位NO性质的影响。给出了1和2的振动光谱（IR和拉曼光谱），并使用同位素取代和法线坐标分析进行了分配。1的力常数为12.53（NO）和2.98 mdyn / A（Fe-NO），2的力常数为11.55（NO）和2.55 mdyn / A（Fe-NO）。再加上NMR结果，这提供了实验证据反式配体的结合减弱了Fe-NO键。1和2的主要绑定方案非常相似。在这两种情况下，Fe-NO亚基都强烈弯曲。将NO的单个pi
• Copper–dioxygen reactivity involved in the formation of µ-oxo [(por)Fe^III–O–Cu^IIL]⁺heterodinuclear complexes (por = porphyrinate, L = tetradentate ligand), and novel synthesis of square-planar Fe^II(por) species
  作者：Alaganandan Nanthakumar、Stephen Fox、Kenneth D. Karlin

  DOI：10.1039/c39950000499

  日期：——

  In the reaction of FeIII(por) species with [LCuI(KMeCN)]+ and O2 to give µ-oxo [(por)FeIII–O–CuIIL]+3(por = porphyrinate, L = tetradentate ligand), copper–dioxygen adducts or their decomposition products must be present, otherwise [(por)FeIII–OH] or [(por)FeIII–O–FeIII(por)] products appear; a novel synthesis ot square-planar FeII(por) is also described.

  在 FeIII(por) 物种与 [LCuI(KMeCN)]+ 和 O2 的反应中，如果不生成铜-二氧化物加合物或其分解产物，则会出现 [(por)FeIII–OH] 或 [(por)FeIII–O–FeIII(por)] 产品；还描述了一种新颖的方形平面 FeII(por) 的合成方法。