[μ-2,3-(5-methoxybenzene-1,4-diol)dithiolato]bis(tricarbonyliron) | 1236834-81-3

• 英文名称: [μ-2,3-(5-methoxybenzene-1,4-diol)dithiolato]bis(tricarbonyliron)
• CAS: 1236834-81-3
• 化学式: C₁₃H₆Fe₂O₉S₂
• 分子量: 482.011
• InChiKey: KKOOJNLGTAKPIZ-UHFFFAOYSA-L

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：

  [μ-2,3-(5-methoxybenzene-1,4-diol)dithiolato]bis(tricarbonyliron) 在 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 二氯甲烷 为溶剂， 反应 1.5h， 以81%的产率得到
  参考文献：
  名称：

  Redox Chemistry of Noninnocent Quinones Annulated to 2Fe2S Cores

  摘要：

  Noninnocent ligands that are electronically coupled to active catalytic sites can influence the redox behavior of the catalysts. A series of (mu-dithiolato)Fe-2(CO)6 complexes, in which the sulfur atoms of the mu-dithiolato ligand are bridged by 5-substituted (Me, OMe, Cl, t-Bu)-1,4-benzoquinones, 1,4-naphthoquinone, or 1,4-anthraquinone, have been synthesized and characterized. In addition, the bisphosphine complex derived from the 1,4-naphthoquinone-bridged complex has also been prepared and characterized. Cyclic voltammetry of these complexes shows two reversible one-electron reductions at potentials 0.2 to 0.5 V less negative than their corresponding parent quinones. In the presence of acetic acid two-electron reductions of the complexes result in conversion of the quinones to hydroquinone moieties. EPR spectroscopic and computational studies of the one-electron-reduced complexes show electron delocalization from the semiquinones to the 2Fe2S moieties, thereby revealing the "noninnocent" behavior of these ligands with these catalysts.

  DOI：

  10.1021/om400913p
• 作为产物：
  描述：

  bis(μ-mercapto)bis(tricarbonyliron) 、 甲氧苯醌 在 哌啶 作用下， 生成 [μ-2,3-(5-methoxybenzene-1,4-diol)dithiolato]bis(tricarbonyliron)
  参考文献：
  名称：

  Redox Chemistry of Noninnocent Quinones Annulated to 2Fe2S Cores

  摘要：

  Noninnocent ligands that are electronically coupled to active catalytic sites can influence the redox behavior of the catalysts. A series of (mu-dithiolato)Fe-2(CO)6 complexes, in which the sulfur atoms of the mu-dithiolato ligand are bridged by 5-substituted (Me, OMe, Cl, t-Bu)-1,4-benzoquinones, 1,4-naphthoquinone, or 1,4-anthraquinone, have been synthesized and characterized. In addition, the bisphosphine complex derived from the 1,4-naphthoquinone-bridged complex has also been prepared and characterized. Cyclic voltammetry of these complexes shows two reversible one-electron reductions at potentials 0.2 to 0.5 V less negative than their corresponding parent quinones. In the presence of acetic acid two-electron reductions of the complexes result in conversion of the quinones to hydroquinone moieties. EPR spectroscopic and computational studies of the one-electron-reduced complexes show electron delocalization from the semiquinones to the 2Fe2S moieties, thereby revealing the "noninnocent" behavior of these ligands with these catalysts.

  DOI：

  10.1021/om400913p

文献信息

• Synthesis of Diiron Hydrogenase Mimics Bearing Hydroquinone and Related Ligands. Electrochemical and Computational Studies of the Mechanism of Hydrogen Production and the Role of O−H···S Hydrogen Bonding
  作者：Jinzhu Chen、Aaron K. Vannucci、Charles A. Mebi、Noriko Okumura、Susan C. Borowski、Matthew Swenson、L. Tori Lockett、Dennis H. Evans、Richard S. Glass、Dennis L. Lichtenberger

  DOI：10.1021/om100396j

  日期：2010.11.8

  Spectroscopic studies suggest the presence of intramolecular hydrogen bonding between the phenolic OH groups and the adjacent sulfur atoms. Computations, which are in good agreement with the electrochemical studies and spectroscopic data, indicate that the hydrogen bonding is most important in the reduced forms of the catalysts. This hydrogen bonding lowers the reduction potential for catalysis but

  报道了一种将氢醌环化为Fe 2 S 2（CO）6部分的新合成方法。哌啶催化Fe 2（μ-SH）2（CO）6之间的多步反应和醌以26-76％的收率提供桥接的加合物。氢醌加合物经历可逆的两电子还原。在乙酸的存在下，这些加合物催化生成的氢的电势比初始可逆还原的电势更负。光谱研究表明在酚羟基和相邻的硫原子之间存在分子内氢键。与电化学研究和光谱数据高度吻合的计算表明，在还原形式的催化剂中氢键是最重要的。该氢键降低了催化的还原电位，但也降低了碱性，并因此降低了催化剂的反应性。