(2S,5R)-1,2,3,4,5-pentakis(2,3,4,5,6-pentafluorophenyl)-2,5-dihydroborole | 1236584-20-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2S,5R)-1,2,3,4,5-pentakis(2,3,4,5,6-pentafluorophenyl)-2,5-dihydroborole
• CAS: 1236584-20-5
• 化学式: C₃₄H₂BF₂₅
• 分子量: 896.161
• InChiKey: UAQIEJAVVRLHEP-OCAPTIKFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.14
• 重原子数：
  60
• 可旋转键数：
  5
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  25

反应信息

• 作为产物：
  描述：

  pentakis(pentafluorophenyl)borole 、 氢气 在 P(C(CH₃)3)3 作用下， 以 CD₂Cl₂ 为溶剂， 生成 (2S,5R)-1,2,3,4,5-pentakis(2,3,4,5,6-pentafluorophenyl)-2,5-dihydroborole
  参考文献：
  名称：

  Dihydrogen Activation by Antiaromatic Pentaarylboroles

  摘要：

  Facile metal-free splitting of molecular hydrogen (H(2)) is crucial for the utilization of H(2) without the need for toxic transition-metal-based catalysts. Frustrated Lewis pairs (FLPs) are a new class of hydrogen activators wherein interactions with both a Lewis acid and a Lewis base heterolytically disrupt the hydrogen hydrogen bond. Here we describe the activation of hydrogen exclusively by a boron-based Lewis acid, perfluoropentaphenylborole. This antiaromatic compound reacts extremely rapidly with H(2) in both solution and the solid state to yield boracyclopent-3-ene products resulting from addition of hydrogen atoms to the carbons a to boron in the starting borole. The disruption of antiaromaticity upon reaction of the borole with H(2) provides a significant thermodynamic driving force for this new metal-free hydrogen-splitting reaction.

  DOI：

  10.1021/ja105075h

文献信息

• Mechanistic Studies on the Metal-Free Activation of Dihydrogen by Antiaromatic Pentarylboroles
  作者：Adrian Y. Houghton、Virve A. Karttunen、Cheng Fan、Warren E. Piers、Heikki M. Tuononen

  DOI：10.1021/ja311842r

  日期：2013.1.16

  The perfluoro- and perprotiopentaphenylboroles 1 and 2 react with dihydrogen to effect H-H bond cleavage and formation of boracyclopentene products. The mechanism of this reaction has been studied experimentally through evaluation of the kinetic properties of the slower reaction between 2 and H(2). The reaction is first-order in both [borole] and [H(2)] with activation parameters of ΔH(‡) = 34(8) kJ/mol

  全氟和全原五苯基硼 1 和 2 与二氢反应以实现 HH 键断裂和硼环戊烯产物的形成。通过评估 2 和 H(2) 之间较慢反应的动力学特性，已经通过实验研究了这种反应的机制。[borole] 和 [H(2)] 中的反应均为一级反应，活化参数为 ΔH(‡) = 34(8) kJ/mol 和 ΔS(‡) = -146(25) J mol(-1 ) K(-1)。观察到 1.10(5) 的最小动力学同位素效应，表明限速过渡状态下 HH 裂解的异步几何。为了解释观察到的产物的立体化学，提出了一种开环/闭环机制，并由建议的中间体的单独合成及其观察到的产物转化来支持。此外，反应机制的广泛 DFT 映射支持该提议的合理性。该研究说明了一种在没有外部碱的情况下通过强主基路易斯酸激活 H(2) 的新机制，这一过程部分由 1 和 2 中硼环的反芳香性驱动。