(5,10,15,20-tetrakis(2,6-difluorophenyl)porphyrinate)FeII | 162257-76-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: (5,10,15,20-tetrakis(2,6-difluorophenyl)porphyrinate)FeII
• 英文别名: tetrakis(2,6-difluorophenyl)porphyrinate(2-)iron(II)；iron(II) tetrakis(2,6-difluorophenyl)porphyrinate；(tetrakis(2,6-difluorophenyl)porphyrinate)Fe(II)；(tetrakis(2,6-difluorophenyl)prophyrinato)Fe(II)；tetrakis(2,6-difluorophenyl)porphyrinatoiron(II)；(tetrakis(2,6-difluorophenyl)porphyrin)iron(II)；Fe(tetrakis(2,6-difluorophenyl)porphinate)
• CAS: 162257-76-3
• 化学式: C₄₄H₂₀F₈FeN₄
• 分子量: 812.504
• InChiKey: KIUXKXLYXKTTJD-AQZHRKEBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
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• 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：

  (5,10,15,20-tetrakis(2,6-difluorophenyl)porphyrinate)FeII 、 氧化亚氮 以 四氢呋喃 为溶剂， 生成 (tetrakis(2,6-difluorophenyl)porphyrinate)Fe^II(NO)
  参考文献：
  名称：

  血红素/非血红素二铁 (II) 复合物和 O2、CO 和 NO 加合物作为细菌一氧化氮还原酶活性位点的还原和底物结合模型

  摘要：

  作为细菌一氧化氮还原酶的反应性还原活性位点形式的第一代模型，血红素/非血红素二铁 (II) 复合物 [(6L)Fe(II)...Fe(II)-(Cl)] + (2) {其中 6L = 部分氟化的四苯基卟啉与束缚的四齿 TMPA 螯合物；TMPA = 三（2-吡啶基）胺}是通过还原相应的 mu-氧代二铁化合物 [(6L)Fe(III)-O-Fe(III)-Cl]+ (1) 生成的。还开发了还原 NOR 与 O2、CO 和 NO 反应的配位化学模型。与 O2 和 CO 形成加合物，[(6L)Fe(III)(O2-))(thf)...Fe(II)-Cl]B(C6F5)4 (2a x O2) {lambda(max) 418（索雷特），536 纳米；nu(OO) = 1176 cm(-1), nu(Fe-O) = 574 cm(-1) 和 [(6L)Fe(II)(CO)(thf)Fe(II)-Cl]B(C6F5)

  DOI：

  10.1021/ja0458773
• 作为产物：
  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+

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。
• 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
• 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、酸和酚类的反应性方面的差异和相似之处。μ-oxo 配合物2a的新 X 射线结构与先前报道的1a
• Tuning the Geometric and Electronic Structure of Synthetic High-Valent Heme Iron(IV)-Oxo Models in the Presence of a Lewis Acid and Various Axial Ligands
  作者：Melanie A. Ehudin、Leland B. Gee、Sinan Sabuncu、Augustin Braun、Pierre Moënne-Loccoz、Britt Hedman、Keith O. Hodgson、Edward I. Solomon、Kenneth D. Karlin

  DOI：10.1021/jacs.9b00795

  日期：2019.4.10

  of the protic Lewis acid, 2,6-lutidinium triflate (LutH+), with (or without) DCHIm. Mössbauer, rR, and XAS spectroscopic data indicated the formation of molecular Lewis acid ferryl adducts (rather than full protonation). The reduction potentials of these novel Lewis acid adducts were bracketed through addition of outer-sphere reductants. The oxidizing capabilities of the ferryl species with or without

  在所涉及的含血红素酶（P-450s、过氧化物酶、过氧化氢酶和细胞色素 c 氧化酶）的催化循环中，观察到或提出了高价弗瑞尔物种（例如 (Por)FeIV=O、Cmpd-II）的关键氧化中间体在生物呼吸和氧化代谢中。在此，制备了各种轴向连接的铁 (IV)-氧代复合物以检查碱基身份的影响。这些是通过添加各种轴向配体（1,5-二环己基咪唑 (DCHIm)、系留咪唑系统和 3,5-二甲氧基苯酚盐和咪唑盐的钠衍生物）产生的。通过紫外-可见光、电子顺磁共振 (EPR)、57Fe Mössbauer、Fe X 射线吸收 (XAS)、和 54/57Fe 共振拉曼 (rR) 光谱以确认它们的形成并比较这些血红素铁 (IV)-氧代物种的电子和几何结构上的轴向配体扰动。穆斯堡尔研究证实，轴向连接的衍生物是铁 (IV) 和六配位配合物。XAS 和 54/57Fe rR 数据与铁氧键的轻微伸长相关，随着轴向配体的捐赠增加。第一个报道的合成
• Spin Interconversion of Heme-Peroxo-Copper Complexes Facilitated by Intramolecular Hydrogen-Bonding Interactions
  作者：Andrew W. Schaefer、Melanie A. Ehudin、David A. Quist、Joel A. Tang、Kenneth D. Karlin、Edward I. Solomon

  DOI：10.1021/jacs.9b00118

  日期：2019.3.27

  Synthetic peroxo-bridged high-spin (HS) heme-(μ-η2:η1-O22-)-Cu(L) complexes incorporating (as part of the copper ligand) intramolecular hydrogen-bond (H-bond) capabilities and/or steric effects are herein demonstrated to affect the complex's electronic and geometric structure, notably impacting the spin state. An H-bonding interaction with the peroxo core favors a low-spin (LS) heme-(μ-η1:η1-O22-)-Cu(L)

  合成的过氧桥联高自旋 (HS) 血红素-(μ-η2:η1-O22-)-Cu(L) 配合物，包含（作为铜配体的一部分）分子内氢键（H 键）功能和/或本文证明空间效应会影响复合物的电子和几何结构，特别是影响自旋状态。与过氧核心的氢键相互作用有利于低自旋（LS）血红素-(μ-η1:η1-O22-)-Cu(L)结构，从而导致自旋态（5坐标）的可逆温度依赖性相互转换HS 到 6 坐标 LS)。即使没有强的跨轴血红素配体，LS 态在低温下仍占主导地位。路易斯碱的添加通过竞争氢键供体抑制了氢键促进的自旋互变，这说明了诱导自旋交叉（SCO）所需的精确氢键相互作用。共振拉曼光谱 (rR) 显示，氢键悬垂物与桥接过氧化物配体相互作用以稳定 LS 态，但不能稳定 HS 态。 H 键（与 Cu 结合的 O 原子）的作用是削弱 OO 键并增强 Fe-O 键，表现出的 ν(MO) 和 ν(OO) 值与具有强供体反式的类似已知