| 1065560-67-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• CAS: 1065560-67-9
• 化学式: C₁₇H₁₇F₂FeN₅O₇
• 分子量: 497.195
• InChiKey: PQPGJYGFXIPJNK-UHFFFAOYSA-J

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 间氯过氧苯甲酸 作用下， 以 乙腈 为溶剂， 反应 0.05h， 生成
  参考文献：
  名称：

  关于强尾氟化四酰氨基大环配体 (TAML) 活化剂的铁 (V) 反应性

  摘要：

  过氧化物的四酰氨基铁大环配体 (TAML) 活化剂的电子性质可以通过分别改变“头”和“尾”大环组分上的取代基进行精细和粗略调整。通过检查带有头 NO2 和尾 F 取代基的 TAML 氧化铁（V）配合物的反应性，人们能够比较显着降低的大环四酰胺供体容量对氢原子提取、氧原子转移等基本过程的影响，以及通过使用先前对更多富电子 TAML 系统的研究进行电子转移。在这里，我们证明了氧化铁（V）形式 3c 可以通过处理 [Fe{4-NO2C6H3-1,2-(N2COCMe2N3CO)2CF2(Fe-N2)(Fe-N3)}(OH2)]-（ 1c) 在 –40 °C 下使用 MeCN 中的间氯过苯甲酸 (mCPBA)。氧化通过μ-氧代[铁(IV)] 2 二聚体的中间体进行。mCPBA 的 FeIII→FeV 转化的总体速率对于 1c 来说略快于其较少富电子前体 [Fe{C6H4-1,2-(N1COCMe2

  DOI：

  10.1002/ejic.201500001
• 作为试剂：
  描述：

  四聚乙醛 在 sodium hypochlorite 、 、 氘代盐酸 作用下， 以 aq. phosphate buffer 、 重水 为溶剂， 反应 80.0h， 生成 溶剂黄146
  参考文献：
  名称：

  Homogeneous Catalysis Under Ultradilute Conditions: TAML/NaClO Oxidation of Persistent Metaldehyde

  摘要：

  TAML activators enable homogeneous oxidation catalysis where the catalyst and substrate (S) are ultradilute (pM-low mu M) and the oxidant is very dilute (high nM-low mM). Water contamination by exceptionally persistent micropollutants (MPs), including metaldehyde (Met), provides an ultradilute catalysis The lour MP concentrations decrease throughout catalysis ideal space for determining the characteristics and utilitarian limits of this With S oxidation (k(II)) and catalyst inactivation (k(i)) competing for the active catalyst. The percentage of substrate converted (%Cvn) can be increased by discovering methods to increase k(II)/k(i) Here we show that NaClO extends catalyst lifetime to increase the Met turnover number (TON) 3-fold compared with H2O2, highlighting the importance of oxidant choice as a design tool in TAML systems. Met oxidation studies (pH 7, D2O, 0.01 M phosphate, 25 degrees C) monitored by H-1 NMR spectroscopy show benign acetic acid as the only significant product. Analysis of TAML/NaClO treated Met solutions employing successive identical catalyst doses revealed that the processes can be modeled by the recently published relationship between the initial and final [S] (S-0 and S-infinity, respectively), the initial [catalyst] (Fe-Tot) and k(II)/k(i). Consequently, this study establishes that Delta S is proportional to So and that the %Cvn is conserved across all catalyst doses in multicatalyst-dose processes because the rate of the k(II) process depends on [5] while that of the ki process does not. A general tool for determining the FeTot required to effect a desired %Cvn is presented. Examination of the dependence of TON on k(II)/k(i) and Fe-Tot at a fixed S-0 indicates that for any TAML process employing Fe-Tot < 1 x 10(-6) M, small catalyst doses are not more efficient than one large dose.

  DOI：

  10.1021/jacs.6b11145

文献信息

• Structural, Mechanistic, and Ultradilute Catalysis Portrayal of Substrate Inhibition in the TAML–Hydrogen Peroxide Catalytic Oxidation of the Persistent Drug and Micropollutant, Propranolol
  作者：Yogesh Somasundar、Longzhu Q. Shen、Alexis G. Hoane、Liang L. Tang、Matthew R. Mills、Abigail E. Burton、Alexander D. Ryabov、Terrence J. Collins

  DOI：10.1021/jacs.8b08108

  日期：2018.9.26

  TAML activators enable unprecedented, rapid, ultradilute oxidation catalysis where substrate inhibitions might seem improbable. Nevertheless, while TAML/H2O2 rapidly degrades the drug propranolol, a micropollutant (MP) of broad concern, propranolol is shown to inhibit its own destruction under concentration conditions amenable to kinetics studies ([propranolol] = 50 mu M). Substrate inhibition manifests as a decrease in the second-order rate constant k(I) for H2O2 oxidation of the resting Fe-III-TAML (RC) to the activated catalyst (AC), while the second-order rate constant k(II) for attack of AC on propranolol is unaffected. This kinetics signature has been utilized to develop a general approach for quantifying substrate inhibitions. Fragile adducts [propranolol, TAML] have been isolated and subjected to ESI-MS, florescence, UV-vis, FTIR, H-1 NMR, and IC examination and DFT calculations. Propranolol binds to Fe-III-TAMLs via combinations of noncovalent hydrophobic, coordinative, hydrogen bonding, and Coulombic interactions. Across four studied TAMLs under like conditions, propranolol reduced k(I) 4-32-fold (pH 7, 25 degrees C) indicating that substrate inhibition is controllable by TAML design. However, based on the measured k(I) and calculated equilibrium constant K for propranolol-TAML binding, it is possible to project the impact on k(I) of reducing [propranolol] from 50 mu M to the ultradilute regime typical of MP contaminated waters (<= 2 ppb, <= 7 nM for propranolol) where inhibition nearly vanishes. Projecting from 50 mu M to higher concentrations, propranolol completely inhibits its own oxidation before reaching mM concentrations. This study is consistent with prior experimental findings that substrate inhibition does not impede TAML/H2O2 destruction of propranolol in London wastewater while giving a substrate inhibition assessment tool for use in the new field of ultradilute oxidation catalysis.