| 213403-81-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• CAS: 213403-81-7
• 化学式: C₆₃H₄₁F₆FeN₈O₂
• 分子量: 1111.91
• InChiKey: WRWIPKWGJHJSKQ-MEAQTMLPSA-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：

  在 sodium dithionite 作用下， 以 not given 为溶剂， 生成 (5-(o-O-[(N,N-bis(2-pyridylmethyl)-2-(6-methoxyl)pyridinemethanamine)phenyl])-10,15,20-tris(2,6-difluorophenyl)porphyrinato)iron(II)
  参考文献：
  名称：

  Dioxygen Reactivity of Fully Reduced [LFe^II···Cu^I]⁺ Complexes Utilizing Tethered Tetraarylporphyrinates:  Active Site Models for Heme-Copper Oxidases

  摘要：

  For O-2-reactivity studies aimed at modeling aspects of heme-copper oxidase enzyme function, use of heterobinucleating ligands (6-pyridyl (L-6) or 5-pyridyl (L-5) connection) gives rise to iron(II) (with "empty-tether"), 2a and 2b, and [LFeII... Cu-I](+) complexes, 3a and 3b, respectively. Reduced complexes 2 and 3 can exist in high-, intermediate-, or low-spin iron(II) configurations, depending on the solvent employed. Reaction of dioxygen with both 3a and 3b leads to a biomimetic reductive O-O bond cleavage forming mu-oxo species [(L)Fe-III-O-Cu-II](+) (4a, 4b). The X-ray structure of 4a is reported.

  DOI：

  10.1021/ic9900511
• 作为产物：
  描述：

  以 二氯甲烷 为溶剂， 生成
  参考文献：
  名称：

  O（2）绑定到（（6）L）Fe（II），一种含亚铁血红素的共价键合轴向吡啶配体的低温UV-可见光和NMR光谱研究。

  摘要：

  在本报告中，我们描述了（（6）L）Fe（II）（1）[（6）L =部分氟化的四苯基卟啉与共价附加的TMPA部分；使用低温UV-vis和多核（（1）H和（2）H）NMR光谱的组合，TMPA =三（2-吡啶基甲基）胺。络合物1或其吡咯氘代类似物（（6）Ld（8））Fe（II）（1-d（8））在所有使用的溶剂中均表现出低场位移的吡咯共振（δ28-60 ppm）[CH（ 2）Cl（2），（CH（3））（2）C（O），CH（3）CN，THF]，即使没有外源性轴向溶剂，也表明具有五配位的高旋转亚铁血红素配体存在（即在二氯甲烷中）。此外，（（6）L）Fe（II）（1）在CH（2）Cl（2），（CH（3））（2）C（O）和CH （3）CN溶剂 我们将其归因于TMPA-吡啶基臂与亚铁血红素的分子内或分子间结合引起的共振。在（193°C）二氯甲烷中于193 K暴露于双氧时，（（6）L）Fe（II）（1）[UV-vis：lambda（max）=

  DOI：

  10.1021/ic0103547
• 作为试剂：
  描述：

  氧气 在 作用下， 生成 水
  参考文献：
  名称：

  Electrocatalytic O₂-Reduction by Synthetic Cytochrome c Oxidase Mimics: Identification of a “Bridging Peroxo” Intermediate Involved in Facile 4e^–/4H⁺ O₂-Reduction

  摘要：

  A synthetic heme-Cu CcO model complex shows selective and highly efficient electrocatalytic 4e(-)/4H(+) O-2-reduction to H2O with a large catalytic rate (>105 s(-1))" While the hemeCu model (Fe Cu) shows almost exclusive 4e(-)/4H(+) r reduction of O-2 to H2O (detected using ring disk electrochemistry and rotating ring disk electrochemistry), when imidazole is bound to the heme (Fe(Irn)Cu), this same selective O-2-reduction to water occurs only under slow electron fluxes. Surface enhanced resonance Raman spectroscopy coupled to dynamic electrochemistry data suggests the formation of a bridging peroxide intermediate during O-2-reduction by both complexes under steady state reaction conditions, indicating that O-O bond heterolysis is likely to be the rate-determining step (RDS) at the mass transfer limited region. The O-O vibrational frequencies at 819 cm(-1) in 1602 (759 cm(-1) in 1802) for the Fe Cu complex and at 847 cm(-1) (786 cm-1) for the Fe(Im)Cu complex, indicate the formation of side-on and end-on bridging Fe-peroxo-Cu intermediates, respectively, during O-2-reduction in an aqueous environment. These data suggest that side-on bridging peroxide intermediates are involved in fast and selective O-2-reduction in these synthetic complexes. The greater amount of H2O2 production by the imidazole bound complex under fast electron transfer is due to 1e(-)/1H(+) O-2-reduction by the distal Cu where O-2 binding to the water bound low spin Fell complex is inhibited.

  DOI：

  10.1021/jacs.5b06513

文献信息

• Wang, Jun; Schopfer, Mark P.; Sarjeant, Amy A. N., Journal of the American Chemical Society, 2009, vol. 131, p. 450 - 451
  作者：Wang, Jun、Schopfer, Mark P.、Sarjeant, Amy A. N.、Karlin, Kenneth D.

  DOI：——

  日期：——
• Intermolecular versus intramolecular electron-/atom- (Cl) transfer in heme-iron and copper pyridylalkylamine complexes
  作者：H. Christopher Fry、Heather R. Lucas、Lev N. Zakharov、Arnold L. Rheingold、Gerald J. Meyer、Kenneth D. Karlin

  DOI：10.1016/j.ica.2007.08.016

  日期：2008.3

  While outer-sphere electron-transfer reactions come with a firm experimental and theoretical basis, less is known about the redox reactions occurring by atom-transfer. In the present study, relevant reactions occur upon mixing, (F-8)Fe-III(Cl) (F-8 is tetrakis(2,6-difluorophenyl)porphyrinate) with a series of [(L)Cu-I](+) complexes (L are tripodal tetradentate pyridylalkylamine ligands varying in effective chelate ring sizes: TMPA, PMEA, PMAP) to form (F-8)Fe-II and [(L)Cu-II(Cl)](+). The electron-/atom- (Cl-center dot) transfer process is characterized by electrochemical measurements as well as UV-Vis, H-1 NMR, and EPR spectroscopies. Stopped-flow UV-Vis spectroscopy in THF indicate the following relative rates (k(obs)) [Cu-I(pmea)](+) > [Cu-I(pmap)](+) > [Cu-I(tmpa)(thf)](+). However, the redox potentials as related to Delta G degrees for the reaction, [E-1/2(oxidant) - E-1/2(reductant)], predict the trend [Cu-I(tmpa)(CH3CN)](+) > [Cu-I(pmea)](+) > [Cu-I(pmap)](+). A detailed description of Cu-I-to-Cu-II structural changes is provided and these likely influence the observed [(L)Cu-I](+)/(F-8)Fe-III(Cl) reaction rates. Analogous chemistry is described for a heme-copper system utilizing a heterobinucleating ligand (L-6), which is comprised of a TMPA like moiety tethered at the 6-position of one of the pyridyl donors to a F-8-like heme. Kinetic/mechanistic insights were obtained from transient absorption spectroscopic monitoring in CH3CN following photoejection of carbon monoxide from [(L-6)Fe-II(CO) center dot center dot center dot Cu-II(Cl)]. (C) 2007 Elsevier B.V. All rights reserved.