hydroxo(meso-tetrakis(2,6-difluorophenyl)porphirinato)iron(III) | 98716-00-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: hydroxo(meso-tetrakis(2,6-difluorophenyl)porphirinato)iron(III)
• 英文别名: tetrakis(2,6-difluorophenylporphinato)hydroxoiron(III)；(tetrakis(2,6-difluorophenyl)porphyrinate)Fe(III)OH；hydroxo(5,10,15,20-tetrakis(2,6-difluorophenyl)porphyrinato)iron(III)；(5,10,15,20-tetrakis(2,6-difluorophenyl)porphyrin(2-))Fe(III)(OH)；[Fe(III)(hydroxo)(tetrakis(2,6-difluorophenyl)porphyrinato)]；[Fe(OH)(tetrakis(2,6-difluorophenyl)porphyrinate(2-))]
• CAS: 98716-00-8
• 化学式: C₄₄H₂₁F₈FeN₄O
• 分子量: 829.511
• InChiKey: IQVQOGDJXZWWDG-TXFZNMFQSA-M

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：

  hydroxo(meso-tetrakis(2,6-difluorophenyl)porphirinato)iron(III) 在 Na₂S₂O₄ 作用下， 以 二氯甲烷 、 水 为溶剂， 以72%的产率得到(5,10,15,20-tetrakis(2,6-difluorophenyl)porphyrinate)FeII
  参考文献：
  名称：

  Oxo- and Hydroxo-Bridged Heme-Copper Assemblies Formed from Acid−Base or Metal−Dioxygen Chemistry

  摘要：

  The iron-copper dinuclear active site in heme-copper oxidases (e.g., cyctochrome c oxidase) has spurred the development of the inorganic: chemistry of bridged heme-copper complexes, including species possessing (porphyrinate)Fe-III-O(H)-Cu-II-L moieties. We describe here the synthesis, by two routes, of [(F8TPP)Fe-III-O-Cu-II(MePY2)](+) (5) {F8TPP = tetrakis(2,6-difluorophenyl)porphyrinate; MePY2 = N,N-bis[2-(2-pyridyl)ethyl] methylamine). First, 5-(CF3SO3) was generated by reaction of [(MePY2)Cu-II](CF3SO3)(2) (3-(CF3SO3)(2)) and [(F8TPP)Fe-III-OH] (4) with triethylamine in THF or CH3CN in 65-70% yield. The complex was also prepared by reduction of O-2 by a 1:1 mixture of copper(I) and iron(II) complexes, [(MePY2)Cu-I(CH3CN)](BArF) (1-(BArF)) (BArF = tetrakis(3,5-bis-trifluoromethylphenyl)borate) and (F8TPP)Fe-II (2) in O-2-saturated THF or acetone, at -80 degrees C with subsequent warming to room temperature. Preliminary stopped-flow kinetics on the O-2 reaction with the 1:1 mixture show the formation of at least two intermediates (i.e., a superoxo species (F8TPP)Fe-O-2 first, and then a presumed peroxo-bridged Fe-O-2-Cu species) prior to the formation of the final mu-oxo complex [(F8TPP)Fe-III-O-Cu-II(MePY2)](+) (5-(BArF)). The H-1 NMR spectrum of 5-(CF3SO3) in CD2Cl2 exhibits a pyrrole peak at 67.7 ppm (corroborated by H-2 NMR), while downfield (23.4 and 18.9 ppm) and dramatically upfield-shifted resonances (-87.7, -155.4 and -189.4) have been assigned to hydrogens of the MePY2 moiety, by specific deuteration. The mu-hydroxo complex [(F8TPP)Fe-(OH)-Cu(MePY2)](OTf)(2) (6-(CF3SO3)(2)) was synthesized by addition of 3-(CF3SO3)(2) to 4 in CH3CN, or by protonation of 5-(CF3SO3) with CF3SO3H. In a H-1. NMR-spectroscopic protonation titration (CF3SO3H)(2) the pyrrole 67.7 ppm resonance for 5-(CF3SO3) progressively converts to 70.3 ppm, diagnostic of 6-(CF3SO3)(2). The protonation is slow on the NMR time scale. The H-1 NMR spectral properties are consistent with antiferromagnetically coupled high-spin iron(III) and Cu(II) ions (S = 2 spin state), and the interaction is weaker in 6-(CF3SO3)(2) (5-(CF3SO3), mu(eff) = 5.05 mu(B); 6-(CF3SO3)(2), mu(eff) = 5.60 mu(B); Evans NMR method). By titration using a series of organic acids, the pK(a) for 6-(CF3S03)2 has been estimated to be 16.7 < pK(a) < 17.6 (CH3CN solvent), or 9.6 +/- 2 (aqueous). Plots of delta vs 1/T for both mu-oxo and mu-hydroxo complexes 5-(CF3SO3) and 6-(CF3SO3)(2) have been obtained, showing linear Curie (for downfield resonances) or anti-Curie (for upfield peaks) behavior.

  DOI：

  10.1021/ic981431+
• 作为产物：
  描述：

  superoxo(tetrakis(2,6-difluorophenyl)porphyrinato)(tetrahydrofuran)iron(III) 在 2,4-di-tert-butylphenol 、 NO 作用下， 以 四氢呋喃 为溶剂， 生成 hydroxo(meso-tetrakis(2,6-difluorophenyl)porphirinato)iron(III)
  参考文献：
  名称：

  血红素/O2/•NO 一氧化氮双加氧酶 (NOD) 反应性：通过假定的血红素-过氧亚硝酸盐中间体进行酚类硝化

  摘要：

  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。

  DOI：

  10.1021/ja904832j

文献信息

• Heme−Copper−Dioxygen Complexes: Toward Understanding Ligand-Environmental Effects on the Coordination Geometry, Electronic Structure, and Reactivity
  作者：Zakaria Halime、Matthew T. Kieber-Emmons、Munzarin F. Qayyum、Biplab Mondal、Thirumanavelan Gandhi、Simona C. Puiu、Eduardo E. Chufán、Amy A. N. Sarjeant、Keith O. Hodgson、Britt Hedman、Edward I. Solomon、Kenneth D. Karlin

  DOI：10.1021/ic9020993

  日期：2010.4.19

  and more complete electronic description of the high-spin heme−peroxo−copper complexes 1 and 2, which establish μ-(O22−) side-on to the FeIII and end-on to CuII (μ-η2:η1) binding for the complex 1 but side-on/side-on (μ-η2:η2) μ-peroxo coordination for the complex 2. We also compare and summarize the differences and similarities of these two complexes in their reactivity toward CO, PPh3, acid, and phenols

  配体的性质是控制配位化学结构和反应性的一个重要方面。结合我们对与细胞色素c氧化酶双氧还原化学相关的血红素-铜-氧反应性的研究，我们比较了两种高自旋血红素-过氧-铜 [Fe III O 2 2- Cu II ] +的分子和电子结构含有 N 4四齿 ( 1 ) 或 N 3三齿 ( 2 ) 的配合物) 铜配体。结合先前报道的和新的共振拉曼和 EXAFS 数据与密度泛函理论计算相结合，我们报告了高自旋血红素-过氧-铜配合物1和2的几何结构和更完整的电子描述，它们建立了 μ-(O 2 2 − ) 侧面与 Fe III和端部与 Cu II (μ-η 2 :η 1 ) 结合，与复合物1结合，但侧面/侧面 (μ-η 2 :η 2 ) μ-peroxo复杂2 的协调. 我们还比较和总结了这两种配合物在对 CO、PPh 3、酸和酚�