(4-di(tert-butyl)phosphonium-2,3,5,6-tetrafluorophenyl)bis(pentafluorophenyl)borohydride

• 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: (4-di(tert-butyl)phosphonium-2,3,5,6-tetrafluorophenyl)bis(pentafluorophenyl)borohydride
• 英文别名: tBu2PHC6F4BH(C6F5)2；Hydrogen [4-di-tert-butylphosphino-2,3,5,6-tetrafluorophenyl]hydrobis(2,3,4,5,6-pentafluorophenyl)borate, 97%；(4-ditert-butylphosphanyl-2,3,5,6-tetrafluorophenyl)-bis(2,3,4,5,6-pentafluorophenyl)boranuide;hydron
• 化学式: C₂₆H₂₀BF₁₄P
• 分子量: 640.207
• InChiKey: KGYHXLYRDXKNBO-UHFFFAOYSA-O

计算性质

• 辛醇/水分配系数(LogP)：
  6.32
• 重原子数：
  42
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  15

反应信息

• 作为反应物：
  描述：

  (4-di(tert-butyl)phosphonium-2,3,5,6-tetrafluorophenyl)bis(pentafluorophenyl)borohydride 以 甲苯 为溶剂， 生成 tBu2P(SPh)C6F4B(C6F5)2(SPh)
  参考文献：
  名称：

  Heterolytic Cleavage of Disulfides by Frustrated Lewis Pairs

  摘要：

  The addition of diphenyl disulfide (PhSSPh) to tBu(2)P(C6F4)B(C6F5)(2) (1) affords the zwitterionic phosphonium borate [tBu(2)P(SPh)(C6F4)B(SPh)(C6F5)(2)] (2), while the addition of a base or donor solvent to 2 effected the liberation of disulfide and the formation of [tBu(2)P(C6F4)B(donor)(C6F5)(2)]. The reaction of 1 with S-8 gave tBu(2)P(S)(C6F4)B(C6F5)(2) (3). In a similar fashion, the frustrated Lewis pair of tBu(3)P/B(C6F5)(3) reacts with RSSR to give [tBu(3)P(SR)][(RS)B(C6F5)(3)] (R = Ph (4), p-tolyl (5), iPr (6)). In contrast, the corresponding reaction of BnSSBn yields a 1:11 mixture of tBu(3)P=S, Bn2S, and B(C6F5)(3). Species 4 reacts with p-tolylSSp-tolyl to give a mixture of 4, 5, PhSSPh, and p-tolylSS p-tolyl, while treatment of 5 with PhSSPh afforded a similar mixture. To probe this, a crossover experiment between [tBu(3)P(SPh)][B(C6F5)(4)] (7) and [NBU4][(P-tolylS)B(C6F5)(3)] (9) was performed. The former species was prepared by a reaction of 4 with [Ph3C][B(C6F5)(4)], while cation exchange of [(Et2O)(2)Li( P-tolylS)B(C6F5)(3)] (8) with [NBu4]Br gave 9. The reaction of Compounds 7 and 9 gave a statistical mixture of the cations [tBu(3)P(SR)](+) and anions [(RS)B(C6F5)(3)](-), R = Ph, Sp-tolyl. The mechanism of this exchange process was probed and is proposed to be an equilibrium involving disulfide and the frustrated Lewis pair. Crystallographic data are reported for compounds 4-8, and the natures of the P-S cations are examined via DFT calculations.

  DOI：

  10.1021/ic901590s
• 作为产物：
  描述：

  二-叔丁基膦 以 二氯甲烷 、 甲苯 为溶剂， 生成 (4-di(tert-butyl)phosphonium-2,3,5,6-tetrafluorophenyl)bis(pentafluorophenyl)borohydride
  参考文献：
  名称：

  使用“沮丧的Lewis对”的反应性来调节Lewis酸度：容易形成膦-硼烷和阳离子formation-硼烷。

  摘要：

  “沮丧的路易斯对”的概念涉及供体和受体位点，在这些位点中，空间拥挤阻止了路易斯酸碱加合物的形成。在空间上需要膦和硼烷的情况下，这种自动猝灭的缺乏促使对B的碳原子发生亲核攻击，然后进行氟化物转移，从而得到两性离子硼酸硼酸盐[R（3）P（C（6）F（4））BF （C（6）F（5））（2）]和[R（2）PH（C（6）F（4））BF（C（6）F（5））（2）]。这些可以很容易地转化成阳离子phospho硼烷[R（3）P（C（6）F（4））B（C（6）F（5））（2）]（+）和[R（2 ）PH（C（6）F（4））B（C（6）F（5））（2）]（+）或进入中性膦硼烷R（2）P（C（6）F（4 ））B（C（6）F（5））（2）。这种新的反应性提供了通往硼烷家族的模块化途径，其中路易斯酸中心的空间特征保持恒定，而取代基的变化为路易斯酸的调节提供了简便的途径。使用Gutmann-Beckett和Childs

  DOI：

  10.1039/b704417h
• 作为试剂：
  描述：

  N-亚苄基-N-(二苯甲基)胺 在 (4-di(tert-butyl)phosphonium-2,3,5,6-tetrafluorophenyl)bis(pentafluorophenyl)borohydride 、 氢气 、 三异丁基铝 作用下， 以 甲苯 为溶剂， 80.0 ℃ 、10.13 MPa 条件下， 反应 18.0h， 生成 N-苄基-(二苯基)甲胺
  参考文献：
  名称：

  Improving the Industrial Feasibility of Metal-Free Hydrogenation Catalysts Using Chemical Scavengers

  摘要：

  A modified process using inexpensive poison scavengers has been developed that allows for more economical and practical scale-up of metal-free catalytic hydrogenation. The scavengers remove impurities such as water and aldehydes that can hinder catalysis allowing for the use of commercial-grade solvents, substrates and gases. In addition, the scavengers have the unique ability to regenerate poisoned catalysts, allowing for increased turnover numbers and longer catalyst lifetimes. Hydrogenations of unpurified imine substrates proceed with high yield using a variety of metal-free hydrogenation catalysts, demonstrating the general compatibility of this process.

  DOI：

  10.1021/op4000847

文献信息

• Metal-Free Catalytic Hydrogenation
  作者：Preston A. Chase、Gregory C. Welch、Titel Jurca、Douglas W. Stephan

  DOI：10.1002/anie.200702908

  日期：2007.10.22
• Dihydrogen Activation with ^<i>t</i>Bu₃P/B(C₆F₅)₃: A Chemically Competent Indirect Mechanism via in Situ-Generated <i>p</i>-^<i>t</i>Bu₂P–C₆F₄–B(C₆F₅)₂
  作者：Adam J. V. Marwitz、Jason L. Dutton、Lauren G. Mercier、Warren E. Piers

  DOI：10.1021/ja203214f

  日期：2011.7.6

  A chemically competent indirect pathway for the activation of dihydrogen by the nonmetal Lewis acid/Lewis base pair (Bu3P)-Bu-t/B(C6F5)(3) is described. The reaction between (Bu3P)-Bu-t and B(C6F5)(3) produces [(Bu3PH)-Bu-t](+)[FB(C6F5)(3)](-) and the known phosphinoborane p-(Bu2P)-Bu-t-C6F4-B(C6F5)(2) (1-Bu-t) with elimination of isobutylene. At 1:1 stoichiometry, 1-Bu-t is produced rapidly in detectable quantities and can act as a catalyst for the formation of [(Bu3PH)-Bu-t](+)[HB(C6F5)(3)](-) from (Bu3P)-Bu-t and B(C6F5)(3) in the presence of H-2. The extent to which this indirect path competes with the direct path is explored.
• Heterolytic Cleavage of Disulfides by Frustrated Lewis Pairs
  作者：Meghan A. Dureen、Gregory C. Welch、Thomas M. Gilbert、Douglas W. Stephan

  DOI：10.1021/ic901590s

  日期：2009.10.19

  The addition of diphenyl disulfide (PhSSPh) to tBu(2)P(C6F4)B(C6F5)(2) (1) affords the zwitterionic phosphonium borate [tBu(2)P(SPh)(C6F4)B(SPh)(C6F5)(2)] (2), while the addition of a base or donor solvent to 2 effected the liberation of disulfide and the formation of [tBu(2)P(C6F4)B(donor)(C6F5)(2)]. The reaction of 1 with S-8 gave tBu(2)P(S)(C6F4)B(C6F5)(2) (3). In a similar fashion, the frustrated Lewis pair of tBu(3)P/B(C6F5)(3) reacts with RSSR to give [tBu(3)P(SR)][(RS)B(C6F5)(3)] (R = Ph (4), p-tolyl (5), iPr (6)). In contrast, the corresponding reaction of BnSSBn yields a 1:11 mixture of tBu(3)P=S, Bn2S, and B(C6F5)(3). Species 4 reacts with p-tolylSSp-tolyl to give a mixture of 4, 5, PhSSPh, and p-tolylSS p-tolyl, while treatment of 5 with PhSSPh afforded a similar mixture. To probe this, a crossover experiment between [tBu(3)P(SPh)][B(C6F5)(4)] (7) and [NBU4][(P-tolylS)B(C6F5)(3)] (9) was performed. The former species was prepared by a reaction of 4 with [Ph3C][B(C6F5)(4)], while cation exchange of [(Et2O)(2)Li( P-tolylS)B(C6F5)(3)] (8) with [NBu4]Br gave 9. The reaction of Compounds 7 and 9 gave a statistical mixture of the cations [tBu(3)P(SR)](+) and anions [(RS)B(C6F5)(3)](-), R = Ph, Sp-tolyl. The mechanism of this exchange process was probed and is proposed to be an equilibrium involving disulfide and the frustrated Lewis pair. Crystallographic data are reported for compounds 4-8, and the natures of the P-S cations are examined via DFT calculations.
• Tuning Lewis acidity using the reactivity of “frustrated Lewis pairs”: facile formation of phosphine-boranes and cationic phosphonium-boranes
  作者：Gregory C. Welch、Lourdes Cabrera、Preston A. Chase、Emily Hollink、Jason D. Masuda、Pingrong Wei、Douglas W. Stephan

  DOI：10.1039/b704417h

  日期：——

  phosphonium-boranes [R(3)P(C(6)F(4))B(C(6)F(5))(2)](+) and [R(2)PH(C(6)F(4))B(C(6)F(5))(2)](+) or into the neutral phosphino-boranes R(2)P(C(6)F(4))B(C(6)F(5))(2). This new reactivity provides a modular route to a family of boranes in which the steric features about the Lewis acidic center remains constant and yet the variation in substitution provides a facile avenue for the tuning of the Lewis acidity. Employing

  “沮丧的路易斯对”的概念涉及供体和受体位点，在这些位点中，空间拥挤阻止了路易斯酸碱加合物的形成。在空间上需要膦和硼烷的情况下，这种自动猝灭的缺乏促使对B的碳原子发生亲核攻击，然后进行氟化物转移，从而得到两性离子硼酸硼酸盐[R（3）P（C（6）F（4））BF （C（6）F（5））（2）]和[R（2）PH（C（6）F（4））BF（C（6）F（5））（2）]。这些可以很容易地转化成阳离子phospho硼烷[R（3）P（C（6）F（4））B（C（6）F（5））（2）]（+）和[R（2 ）PH（C（6）F（4））B（C（6）F（5））（2）]（+）或进入中性膦硼烷R（2）P（C（6）F（4 ））B（C（6）F（5））（2）。这种新的反应性提供了通往硼烷家族的模块化途径，其中路易斯酸中心的空间特征保持恒定，而取代基的变化为路易斯酸的调节提供了简便的途径。使用Gutmann-Beckett和Childs
• Improving the Industrial Feasibility of Metal-Free Hydrogenation Catalysts Using Chemical Scavengers
  作者：Jordan W. Thomson、Jillian A. Hatnean、Jeff J. Hastie、Andrew Pasternak、Douglas W. Stephan、Preston A. Chase

  DOI：10.1021/op4000847

  日期：2013.10.18

  A modified process using inexpensive poison scavengers has been developed that allows for more economical and practical scale-up of metal-free catalytic hydrogenation. The scavengers remove impurities such as water and aldehydes that can hinder catalysis allowing for the use of commercial-grade solvents, substrates and gases. In addition, the scavengers have the unique ability to regenerate poisoned catalysts, allowing for increased turnover numbers and longer catalyst lifetimes. Hydrogenations of unpurified imine substrates proceed with high yield using a variety of metal-free hydrogenation catalysts, demonstrating the general compatibility of this process.