pentakis(pentafluorophenyl)borole | 1160503-52-5

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: pentakis(pentafluorophenyl)borole
• 英文别名: perfluoropentaphenylborole；1,2,3,4,5-Pentakis(2,3,4,5,6-pentafluorophenyl)borole；1,2,3,4,5-pentakis(2,3,4,5,6-pentafluorophenyl)borole
• CAS: 1160503-52-5
• 化学式: C₃₄BF₂₅
• 分子量: 894.145
• InChiKey: LXZJIJBXRYMXFO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.18
• 重原子数：
  60
• 可旋转键数：
  5
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  25

反应信息

• 作为反应物：
  描述：

  pentakis(pentafluorophenyl)borole 在 氢气 作用下， 反应 96.33h， 生成
  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
• 作为产物：
  描述：

  1-Bromo-2,3,4,5-tetrakis(2,3,4,5,6-pentafluorophenyl)borole 、 bis(pentafluorophenyl)zinc 以 甲苯 为溶剂， 以80%的产率得到pentakis(pentafluorophenyl)borole
  参考文献：
  名称：

  Huynh, Keith; Vignolle, Joan; Tilley, T. Don, Angewandte Chemie - International Edition, 2009, vol. 48, p. 2835 - 2837

  摘要：

  DOI：

文献信息

• Divergent Reactivity of Perfluoropentaphenylborole with Alkynes
  作者：Cheng Fan、Warren E. Piers、Masood Parvez、Robert McDonald

  DOI：10.1021/om100334r

  日期：2010.11.8

  Minor products in this reaction were identified as diphenyl-substituted borepins resulting from the Diels−Alder reaction channel. Finally, 3-hexyne reacts with 1 via the Diels−Alder pathway, but the kinetic products are not the expected diethyl borepins but rather one of the initial Diels−Alder adducts formed prior to ring-opening to the seven-membered borepin ring. This intermediate was fully characterized

  已探索了全氟五苯基硼烷（1）与对称内部炔烃RCCR（R = C 6 F 5，C 6 H 5，CH 2 CH 3）的反应。对于R = C 6 F 5，通过为非氟化系统建立的Diels-Alder途径发生缓慢反应，从而生成新的硼烷全氟庚基苯基硼异戊酸酯2。在结晶学上表征了新的全氟芳基硼烷2及其吡啶加合物2-py。相反，反应1与二苯基乙炔的反应主要由反应路径进行，在该反应路径中，硼以亲电子方式攻击炔烃，从而触发1,2苯基迁移和硼环膨胀，从而以主要产物硼环己二烯3的形式传递。在该反应中的次要产物被鉴定为是由Diels-Alder反应通道产生的二苯基取代的硼异氰酸酯。最终，3-己炔通过Diels-Alder途径与1反应，但动力学产物不是预期的二乙基硼销，而是在七元硼销环开环之前形成的初始Diels-Alder加合物之一。该中间体已得到充分表征，并为Eisch提出的有关五苯基硼烷与二苯基乙炔反应的周环反应序列提供了具体证据。
• 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。
• Fan, Cheng; Piers, Warren E.; Parvez, Masood, Angewandte Chemie - International Edition, 2009, vol. 48, p. 2955 - 2958
  作者：Fan, Cheng、Piers, Warren E.、Parvez, Masood

  DOI：——

  日期：——
• Dihydrogen Activation by Antiaromatic Pentaarylboroles
  作者：Cheng Fan、Lauren G. Mercier、Warren E. Piers、Heikki M. Tuononen、Masood Parvez

  DOI：10.1021/ja105075h

  日期：2010.7.21

  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.
• Huynh, Keith; Vignolle, Joan; Tilley, T. Don, Angewandte Chemie - International Edition, 2009, vol. 48, p. 2835 - 2837
  作者：Huynh, Keith、Vignolle, Joan、Tilley, T. Don

  DOI：——

  日期：——