Mes2P-C6F4-B(C6F5)2

• 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: Mes2P-C6F4-B(C6F5)2
• 英文别名: [4-Bis(2,3,4,5,6-pentafluorophenyl)boranyl-2,3,5,6-tetrafluorophenyl]-bis(2,4,6-trimethylphenyl)phosphane
• 化学式: C₃₆H₂₂BF₁₄P
• 分子量: 762.333
• InChiKey: MGPJHUNAOXEFRO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.76
• 重原子数：
  52
• 可旋转键数：
  6
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  14

反应信息

• 作为反应物：
  描述：

  Mes2P-C6F4-B(C6F5)2 、 CpTi(NPt-Bu3)Me2 以 further solvent(s) 为溶剂， 生成 [CpTi(methyl)(NP(t-Bu)3)][Mes2P(C6F4)B(C6F5)2]
  参考文献：
  名称：

  用于烯烃聚合的位阻膦和phospho基活化剂和添加剂。

  摘要：

  形式为[R3PH] [B（C6F5）4]，R2PHC6F4BF（C6F5）2和R2PHC4H8OB（C6F5）3的硼酸phospho以及膦硼烷R2PC6F4B（C6F5）2活化CpTiMe2（NPtBu3）的能力通过化学计量反应和催化性能都检查了聚合反应。通常，尽管产生了游离的膦供体，但这些活化剂仍能产生高活性的乙烯聚合催化剂。将膦添加到催化剂体系中的独立实验表明，预期的小膦活性降低。然而，在空间受限的膦的情况下，观察到活性显着增加。在“沮丧的刘易斯对”概念的背景下考虑了这种增加的原因。

  DOI：

  10.1039/b911489k
• 作为产物：
  描述：

  二(2,4,6-三甲基苯基)膦 在 甲基溴化镁 作用下， 以 乙醚 、 甲苯 为溶剂， 反应 24.0h， 生成 Mes2P-C6F4-B(C6F5)2
  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

文献信息

• Ni, Pd, Pt, and Ru Complexes of Phosphine-Borate Ligands
  作者：Stephanie L. Granville、Gregory C. Welch、Douglas W. Stephan

  DOI：10.1021/ic2026895

  日期：2012.4.16

  8, SIMes 9). While [C10H6N2(Me)4H][tBu2PC6F4BF(C6F5)2] 10 was also prepared. A third strategy for formation of a metal complex of anionic phosphine-borate derivatives was demonstrated in the reaction of (COD)PtMe2 with the neutral phosphine-borane Mes2PC6F4B(C6F5)2 affording (COD)PtMe(Mes2PC6F4BMe(C6F5)2) 11. Extension of this reactivity to tBu2PH(CH2)4OB(C6F5)3) was demonstrated in the reaction with

  物种Cy 2 PHC 6 F 4 BF（C 6 F 5）2与Pt（PPh 3）4反应生成新产物顺式-（PPh 3）2 PtH（Cy 2 PC 6 F 4 BF（C 6 F 5））2）1通过硼酸rate的P–H键的氧化加成到Pt（0）。与Pd（PPh 3）4的相应反应得到1的Pd类似物，即顺式-（PPh 3）2 PdH（Cy 2 PC 6 F 4 BF（C 6 F 5）2）3 ; 硼酸phospho的改性得到盐[（PPh 3）3 PtH] [（t Bu 2 PC 6 F 4 BF（C 6 F 5）2）] 2。或者，硼酸phospho的初始去质子化得到[ t Bu 3 PH] [Cy 2 PC 6 F 4 BF（C6 F 5）2 ] 4，[SIMesH] [Cy 2 PC 6 F 4 BF（C 6 F 5）2 ] 5与NiCl 2（DME）反应生成[BaseH] 2 [反式-Cl 2 Ni（Cy
• Deprotonation and Addition Reactions of Frustrated Lewis Pairs with Alkynes
  作者：Meghan A. Dureen、Christopher C. Brown、Douglas W. Stephan

  DOI：10.1021/om1009044

  日期：2010.12.13

  Deprotonation of terminal alkynes is effected by the treatment with tBu(3)P and B(C6F5)(3) to give [tBu(3)PH][PhCCB(C6F5)(3)] (la) and [tBu(3)PH][RCCB(C6F5)(3)] (R = nBu 2, tBu 3, Me3Si 4, and CpFe(C5H4)5). In a similar fashion, FLP deprotonation of 1,4-diethynylbenzene was employed to prepare the salt [tBu(3)PH](2)[(C6F5)(3)BCC(C6H4)CCB(C6F5)(3)](6). As well, use of differing Lewis acids afforded the species [tBu(3)PH][PhCCEAr3] (EAr3 = Al(C6F5)(3) 7, PhB(C6F5)(2) 8, BPh3 9). The corresponding reaction of Me3SiCCSiMe3 afforded [tBu(3)PSiMe(3)][Me3SiCCB(C6F5)(3)] (10). For less basic phosphines, phosphine/borane addition reactions were observed with alkynes. Thus the species E-R3P(Ph)C=C(H)B(C6F5)(3) (R = o-tol 11, Ph 12) were prepared. In the latter case, Ph3P center dot B(C6F5)(3) was employed. Similarly, E-Ph3P(CPFe(C5H4))C=C(H)B(C6F5)(3) (13), E-Ph3P(Ph)C=C(Me)B(C6F5)(3) (14), E-R2PH(Ph)C=C(H)B(C6F5)(3) (R = Ph 15, C6H2Me3 16), and E-(C(6)H(2)tEu(3))PH2(Ph)C=C(H)B(C6F5)3 (17) were prepared. Again, variation in the Lewis acid afforded E-Ph3P(Ph)C=C(H)EAr3 (EAr3 = PhB(C6F5)(2) 18, Al(C6F5)(3) 19), E-Ph3P(nBu)C=C(H)Al(C6F5)(3) (20), and E-(otol)(3)P(Ph)C= C(H)Al(C6F5)(3) (21). The macrocyclic [(H)C=C(Ph)Mes(2)PC(6)F(4)B(C6F5)(2)](2) (22) was prepared from the analogous alkyne addition to Mes(2)PC(6)F(4)B(C6F5)(2), while E-Ph2PCH2CH7PPh2-(Ph)C=C(H)B(C6F5)(3)(23) and E-(CH2PPh2(Ph)C=C(H)B(C6F5)(3))(2) (24) were derived from the reactions of Ph2PCH2CH2PPh2. The related addition reaction involving 1,4-diethynylbenzene gave E-HC CC6H4C(PPh3)=C(H)B(C6F5)(3) (25), while subsequent reaction with tBu(3)P and B(C6F5)(3) yielded the unusual salt/zwitterion [tBu(3)PH][(C6F5)(3)BCC C6H4C(PPh3)=C(H)-B(C(6)Fs)(3)] (26).Reaction of PhCH2NMe2 with PhCCH and B(C6F5)(3) gave give a 84:16 mixture of [PhCH2NMe2H][PhCCB(C6F5)(3)] (27a) and PhCH2NMe2(Ph)C=C(H)B(C6F5)(3) (27b), while imines were used to prepare [(tBu)HN=CHPh][PhCCB(C6F5)(3)] (28) and [(tBu)HN=CPh2][PhCC(C6F5)(3)] (29). The corresponding reaction of tBuNCNtBu, B(C6F5)(3), and two equivalents of PhCCH led to the unusual product [tBuNCN(H)C(Ph)=C(H)tBu][PhCCB(C6F5)(3)] (30). Finally, non-pnictogen Lewis bases were explored. The reaction of the N-heterocyclic carbene ItBu with B(C6F5)(3) and PhCCH was shown to yield the deprotonation product [ItBuFl][PhCCB(C6F5)(3)] (31), while the sulfides R2S gave E-R2S(Ph)C=C(H)B(C6F5)(3)(R = Me 32, PhCH2 33). The formation of these latter sulfide zwitterions was demonstrated to be reversible.
• 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
• 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
• Sterically hindered phosphine and phosphonium-based activators and additives for olefin polymerization
  作者：Jenny S. J. McCahill、Gregory C. Welch、Douglas W. Stephan

  DOI：10.1039/b911489k

  日期：——

  The ability of phosphonium borates of the form [R3PH][B(C6F5)4], R2PHC6F4BF(C6F5)2 and R2PHC4H8OB(C6F5)3 as well as the phosphine-boranes R2PC6F4B(C6F5)2 to activate CpTiMe2(NPtBu3) for olefin polymerization was examined via both stoichiometric reactions and catalytic performance. In general these activators resulted in highly active ethylene polymerization catalysts, despite the generation of liberated

  形式为[R3PH] [B（C6F5）4]，R2PHC6F4BF（C6F5）2和R2PHC4H8OB（C6F5）3的硼酸phospho以及膦硼烷R2PC6F4B（C6F5）2活化CpTiMe2（NPtBu3）的能力通过化学计量反应和催化性能都检查了聚合反应。通常，尽管产生了游离的膦供体，但这些活化剂仍能产生高活性的乙烯聚合催化剂。将膦添加到催化剂体系中的独立实验表明，预期的小膦活性降低。然而，在空间受限的膦的情况下，观察到活性显着增加。在“沮丧的刘易斯对”概念的背景下考虑了这种增加的原因。