bis(1,4,7-trithiacyclononane)iron(II) | 97391-11-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 金属杂环化合物
• 英文名称: bis(1,4,7-trithiacyclononane)iron(II)
• 英文别名: {Fe({9}aneS3)2}(2+)
• CAS: 97391-11-2
• 化学式: C₁₂H₂₄FeS₆
• 分子量: 416.566
• InChiKey: XRWVUULMGPUYCO-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：

  bis(1,4,7-trithiacyclononane)iron(II) 在 NOBF₄ 作用下， 以 硫酸 为溶剂， 以>99的产率得到{Fe({9}aneS3)2}(ClO4)3*2(H3O(1+)*ClO4(1-))*2HCl*HClO4
  参考文献：
  名称：

  硫醚大环络合物中的π效应：低旋转Fe III硫醚络合物[Fe（[9] aneS 3）2 ] 3+的稳定性和结构

  摘要：

  的[Fe（[9] ANES氧化3）2 ] 2+到的[Fe（[9] ANES 3）2 ] 3+导致的伸长中的Fe-S键的从2.251（1），2.241（1）， 2+阳离子中的2.259（1）Å至3+阳离子中的2.280（3），2.2846（25），2.276（25）Å首次为硫醚冠的π-受体性质提供了直接的结构证据。

  DOI：

  10.1039/c39890001433
• 作为产物：
  描述：

  bis(1,4,7-trithiacyclononane)iron(III) perchlorate 在 H₂O₂ 作用下， 以 水 为溶剂， 生成 bis(1,4,7-trithiacyclononane)iron(II)
  参考文献：
  名称：

  Küppers, Heinz-Josef; Wieghardt, Karl; Nuber, Bernhard, Inorganic Chemistry, 1987, vol. 26, # 22, p. 3762 - 3769

  摘要：

  DOI：

文献信息

• Oxidations of hydrogen peroxide by bis(1,4,7-triazacyclononane)nickel(III), bis(1,4,7-trithiacyclononane)iron(III) and tris(2,2′-bipyridine)ruthenium(III) ions in acidic aqueous solutions ‡
  作者：Nobuyoshi Koshino、Shigenobu Funahashi、Hideo D. Takagi

  DOI：10.1039/a703670a

  日期：——

  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.