| 1018123-37-9

• 分子结构分类: 有机化合物 - 苯类化合物
• CAS: 1018123-37-9
• 化学式: C₁₉H₂₆FeN₄O₆
• 分子量: 462.286
• InChiKey: CKCAYKDDMNMWLL-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

• 作为产物：
  描述：

  thioanisole 、 水 在 茴香硫醚 作用下， 以 aq. phosphate buffer 为溶剂， 生成
  参考文献：
  名称：

  Kinetic and mechanistic studies of the reactivity of iron(IV) TAMLs toward organic sulfides in water: resolving a fast catalysis versus slower single-turnover reactivity dilemma

  摘要：

  TAML complex [Fe-III{C6H4-1,2-(NCOCMe2NCO)(2)CMe2}OH2](-) (1) is oxidized by H2O2 or tBuOOH in water at pH < 10 into the corresponding iron(IV) mu-oxo-bridged dimer 2, which oxidizes readily ring-substituted thioanisoles p-XC6H4SMe (X=H, MeO, Me, Cl, CN) into the corresponding sulfoxides with regeneration of 1. The oxidation studied under pseudo-first-order conditions using the stopped-flow technique by monitoring the fading of the 420-nm band of 2 follows hyperbolic kinetics according to the rate law k(obs) = ab[p-XC6H4SMe]/(1 + b[p-XC6H4SMe]) at pH 8 and 25 degrees C. Parameters a, b, and ab all decrease for electron-poorer thioanisoles and the Hammett value. rho similar to 1 has been found for ab, which can be associated with the second-order rate constants for oxidation of thioanisoles by 2. The kinetics of oxidation of p-NO2C6H4SMe by H2O2 catalyzed by 1 has been studied under steady-state conditions. Covering the concentration of 1 in a 100-fold range has revealed that though first-order kinetics in 1 is observed at low catalyst concentrations (below 10(-6) M), there is a significant negative deviation from linearity at [1] > 10(-6) M. The latter was rationalized by the equilibrium between the monomeric and dimeric Fe-IV species 2 M reversible arrow M-M (K-d), both being able to oxidize p-NO2C6H4SMe with rate constants k(m) and k(d) which were found to be (13 +/- 1) x 10(4) and (0.32 +/- 0.01) x 10(4) M-1 s(-1), respectively. The difference in the rate constants is the key for resolving the dilemma of faster catalysis versus slower single-turnover reactivity of TAML activators in water.

  DOI：

  10.1080/00958972.2015.1065974
• 作为试剂：
  描述：

  4-甲氧基茴香硫醚 在 、 双氧水 作用下， 以 aq. phosphate buffer 为溶剂， 生成 1-methoxy-4-(methylsulfinyl)benzene
  参考文献：
  名称：

  Kinetic and mechanistic studies of the reactivity of iron(IV) TAMLs toward organic sulfides in water: resolving a fast catalysis versus slower single-turnover reactivity dilemma

  摘要：

  TAML complex [Fe-III{C6H4-1,2-(NCOCMe2NCO)(2)CMe2}OH2](-) (1) is oxidized by H2O2 or tBuOOH in water at pH < 10 into the corresponding iron(IV) mu-oxo-bridged dimer 2, which oxidizes readily ring-substituted thioanisoles p-XC6H4SMe (X=H, MeO, Me, Cl, CN) into the corresponding sulfoxides with regeneration of 1. The oxidation studied under pseudo-first-order conditions using the stopped-flow technique by monitoring the fading of the 420-nm band of 2 follows hyperbolic kinetics according to the rate law k(obs) = ab[p-XC6H4SMe]/(1 + b[p-XC6H4SMe]) at pH 8 and 25 degrees C. Parameters a, b, and ab all decrease for electron-poorer thioanisoles and the Hammett value. rho similar to 1 has been found for ab, which can be associated with the second-order rate constants for oxidation of thioanisoles by 2. The kinetics of oxidation of p-NO2C6H4SMe by H2O2 catalyzed by 1 has been studied under steady-state conditions. Covering the concentration of 1 in a 100-fold range has revealed that though first-order kinetics in 1 is observed at low catalyst concentrations (below 10(-6) M), there is a significant negative deviation from linearity at [1] > 10(-6) M. The latter was rationalized by the equilibrium between the monomeric and dimeric Fe-IV species 2 M reversible arrow M-M (K-d), both being able to oxidize p-NO2C6H4SMe with rate constants k(m) and k(d) which were found to be (13 +/- 1) x 10(4) and (0.32 +/- 0.01) x 10(4) M-1 s(-1), respectively. The difference in the rate constants is the key for resolving the dilemma of faster catalysis versus slower single-turnover reactivity of TAML activators in water.

  DOI：

  10.1080/00958972.2015.1065974