bis(1,4,7-trithiacyclononane)iron(III) | 110487-49-5

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: bis(1,4,7-trithiacyclononane)iron(III)
• CAS: 110487-49-5
• 化学式: C₁₂H₂₄FeS₆
• 分子量: 416.566
• InChiKey: WRTSOGURIDJTCO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  19.0
• 可旋转键数：
  0.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  双氧水 、 bis(1,4,7-trithiacyclononane)iron(III) 以 further solvent(s) 为溶剂， 生成 氢气 、 氧气 、 bis(1,4,7-trithiacyclononane)iron(II)
  参考文献：
  名称：

  双（1,4,7-三氮杂环壬烷）镍（III），双（1,4,7-三硫代环壬烷）铁（III）和三（2,2'-联吡啶）钌（III）离子对过氧化氢的氧化作用酸性水溶液‡

  摘要：

  The oxidations of hydrogen peroxide by typical outer-sphere oxidizing reagents, bis(1,4,7-triazacyclononane)nickel(III)[Ni(tacn)(2)(3+)], bis(1,4,7-trithiacyclononane)iron(III)[Fe(ttcn)(2)(3+)], and tris(2,2'-bipyridine)ruthenium(III)[Ru(bipy)(3)(3+)], were studied in acidic aqueous solution [ionic strength I=0.10 mol dm(-3)(NaClO4)]. The stoichiometry was determined iodometrically as 2:1([M-III]:[H2O3]) for the reactions of [Ni(tacn)(2)](3+) and [Fe(ttcn)(2)](3+). Kinetic measurements with an excess of H2O2 revealed that HO2- is the only redox-active species for the reaction with [Ni(tacn)(2)](3+) under the conditions 2 < -log[H+]<5.5, while the participation of both HO2- and H2O2 was observed for the reactions with [Fe(ttcn)(2)](3+) and [Ru(bipy)(2)](3+). The second-order rate constant for the oxidation reaction of HO2- by Ni(tacn)(2)(3+) was (6.15+/-0.06) x 10(6) dm(3) mol(-1) s(-1) at 25 degrees C with Delta H-double dagger=46.9+/-0.4 kJ mol(-1) and Delta S-double dagger=42+/-1 J K-1 mol(-1). The rate constants for the oxidation of HO2- and H2O2 by [Fe(ttcn)(2)](3+) at 25 degrees C were (2.63+/-0.18) x 10(9) dm(3) mol(-1) s(-1) with Delta H-double dagger=26.7+/-4.1 kJ mol(-1) and Delta S-double dagger=25+/-14 J K-1 mol(-1), and 3.12+/-0.03 dm(3) mol(-1) s(-1) with Delta H-double dagger=40.1+/-0.9 kJ mol(-1) and Delta S-double dagger=-101+/-3 J K-1 mol(-1), respectively. The rate constants for the oxidation reaction of HO2- and H2O2 by [Ru(bipy)(3)](3+) at 25 degrees C were (3.70+/-0.26) x 10(7) and 3.57+/-0.19 dm(3) mol(-1) s(-1), respectively It was confirmed from the Marcus-type cross-relation that the oxidations of HO2- by [Fe(ttcn)(2)](3+) and [Ru(bipy)(3)](3+) proceed through the outer-sphere mechanism with k(ex)(HO2.-HO2-)=3.8x10(-3) dm(3) mol(-1) s(-1). The second-order rate constant for the oxidation of HO2- by [Ni(tacn)(2)](3) was ca. 10(3) times faster than the predicted rate constant from the other outer-sphere reactions. The kinetic isotope effect (kH/k(D)=2.8) indicates that the reaction of HO2- with [Ni(tacn)(2)](3+) proceeds via a transition state (shown in Scheme 1). The difference in the reactivity of small ions is discussed in relation to the electronic coupling in the precursor complex and the solvation structures of small ions.

  DOI：

  10.1039/a703670a