[Fe2(μ-H)[(SCH2)2NCH2C6H5](CO)3(cis-1,2-bis(diphenylphosphino)ethylene)(PMe3)][B(C6H3-3,5-(CF3)2)4] | 1308781-92-1

• 英文名称: [Fe2(μ-H)[(SCH2)2NCH2C6H5](CO)3(cis-1,2-bis(diphenylphosphino)ethylene)(PMe3)][B(C6H3-3,5-(CF3)2)4]
• 英文别名: [Fe2(μ-H)((SCH2)2NCH2Ph)(CO)3(PMe3)(cis-1,2-bis(diphenylphosphino)ethylene)][B(C6H3-3,5-(CF3)2)4]
• CAS: 1308781-92-1
• 化学式: C₃₂H₁₂BF₂₄*C₄₁H₄₃Fe₂NO₃P₃S₂
• 分子量: 1729.76
• InChiKey: DGOASGZNCHUOIV-AHGZRVGASA-L

计算性质

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

• 作为产物：
  描述：

  [Fe2[(SCH2)2NHCH2C6H5](CO)3(cis-1,2-bis(diphenylphosphino)ethylene)(PMe3)][B(C6H3-3,5-(CF3)2)4] 以 二氯甲烷 为溶剂， 生成 [Fe2(μ-H)[(SCH2)2NCH2C6H5](CO)3(cis-1,2-bis(diphenylphosphino)ethylene)(PMe3)][B(C6H3-3,5-(CF3)2)4]
  参考文献：
  名称：

  氮杂二硫醇辅因子在 [FeFe]-氢化酶模型中的作用：新结构和催化意义

  摘要：

  本文总结了对 [FeFe]-氢化酶合成模型氧化还原行为的研究，该模型由带有胺辅因子的二铁二硫醇羰基配合物及其 N-苄基衍生物组成。特别感兴趣的是氧化模型对 H(2) 的低反应性的原因，这与这些酶对 H(2) 氧化的高活性形成对比。模型配合物的氧化还原和酸碱性质 [Fe(2)[(SCH(2))(2)NR](CO)(3)(dppv)(PMe(3))](+) ([2 ](+) 表示 R = H 和 [2'](+) 表示 R = CH(2)C(6)H(5)，dppv = cis-1,2-bis(diphenylphosphino)ethylene)) 表示加成H(2) 之后去质子化是 (i) 混合价 (Fe(II)Fe(I)) 状态的吸热和 (ii) 二亚铁 (Fe(II)Fe(II)) 状态的放热。就胺与 Fe 的配位而言，二铁状态被证明是不稳定的，其衍生物的结晶学特征。混合价模型的氧化还原和酸

  DOI：

  10.1021/ja103998v

文献信息

• Hydrogen Activation by Biomimetic Diiron Dithiolates
  作者：Matthew T. Olsen、Bryan E. Barton、Thomas B. Rauchfuss

  DOI：10.1021/ic900850u

  日期：2009.8.17

  Using the thermally stable salts of [Fe-2(SR)(2)(CO)(3)(PMe3)(dppv)]-BAr4F, we found that the azadithiolates [Fe-2(adtR)(CO)(3)(PMe3)-(dppv)](+) react with high pressures of H-2 to give the hydride [Fe-2(mu-H)(adtR)(CO)(3)(dppv)(PMe3)]BAr4F. The related oxadithiolate and propanedithiolate complexes are unreactive toward H-2. Molecular hydrogen is proposed to undergo heterolysis assisted by the amine followed by isomerization of an initially formed terminal hydride. Use of H-2 and D2O gave the deuteride as well as the hydride, implicating protic intermediates.
• Mild Redox Complementation Enables H₂ Activation by [FeFe]-Hydrogenase Models
  作者：James M. Camara、Thomas B. Rauchfuss

  DOI：10.1021/ja201731q

  日期：2011.6.1

  Mild oxidants such as [Fe(C5Me5)(2)](+) accelerate the activation of H-2 by [Fe-2[(SCH2)(2)NBn](CO)(3)-(dppv)(PMe3)](+) ([1](+)), despite the fact that the ferrocenium cation is incapable of oxidizing [1](+). The reaction is first-order in [1](+) and [H-2] but independent of the E-1/2 and concentration of the oxidant. The analogous reaction occurs with D-2 and proceeds with an inverse kinetic isotope effect of 0.75(8). The activation of H-2 is further enhanced with the tetracarbonyl [Fe-2[(SCH2)(2)NBn](CO)(4)(dppn)](+) ([2](+)), the first crystallographically characterized model for the H-ox of the active site containing an amine cofactor. These studies point to rate-determining binding of H-2 followed by proton-coupled electron transfer. Relative to that by [1](+), the rate of H-2 activation by [2](+)/Fc(+) is enhanced by a factor of 10(4) at 25 degrees C.