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