[tBu3PH][PhCCB(C6F5)3] | 1163274-91-6

• 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: [tBu3PH][PhCCB(C6F5)3]
• 英文别名: Tritert-butylphosphanium;tris(2,3,4,5,6-pentafluorophenyl)-(2-phenylethynyl)boranuide
• CAS: 1163274-91-6
• 化学式: C₁₂H₂₇P*C₂₆H₅BF₁₅*H
• 分子量: 816.441
• InChiKey: UIEGPDYVRVDEHT-UHFFFAOYSA-O

计算性质

• 辛醇/水分配系数(LogP)：
  10.43
• 重原子数：
  55
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  16

反应信息

• 作为反应物：
  描述：

  [tBu3PH][PhCCB(C6F5)3] 以 further solvent(s) 为溶剂， 生成 (E)-tBu3PC(Ph)CB(C6F5)3
  参考文献：
  名称：

  Deprotonation and Addition Reactions of Frustrated Lewis Pairs with Alkynes

  摘要：

  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.

  DOI：

  10.1021/om1009044
• 作为产物：
  描述：

  三叔丁基膦 、 (E)-(PhCH2)2SC(Ph)CHB(C6F5)3 以 not given 为溶剂， 生成 [tBu3PH][PhCCB(C6F5)3] 、 (E)-tBu3PC(Ph)CB(C6F5)3
  参考文献：
  名称：

  Deprotonation and Addition Reactions of Frustrated Lewis Pairs with Alkynes

  摘要：

  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.

  DOI：

  10.1021/om1009044

文献信息

• Activation of Terminal Alkynes by Frustrated Lewis Pairs
  作者：Chunfang Jiang、Olivier Blacque、Heinz Berke

  DOI：10.1021/om9008636

  日期：2010.1.11

  The reactions of frustrated Lewis pairs (FLPs) derived from B(C6F5)3 and the bulky Lewis bases 2,2,6,6-tetramethylpiperidine (TMP), tri-tert-butylphosphine, and lutidine (Lut) with terminal alkynes (acetylene, phenylacetylene, 3-ethynylthiophene) were investigated. The FLPs TMP···B(C6F5)3,t-Bu3P···B(C6F5)3 and Lut···(C6F5)3 reacted with acetylene (HC≡CH) to yield the apparently thermodynamically more

  受挫路易斯双（FLP信号）为B（C导出的反应6 ˚F 5）3和笨重的路易斯碱-2,2,6,6-四甲基哌（TMP），三-叔丁基膦，和二甲基吡啶（甩）与终端研究了炔烃（乙炔，苯乙炔，3-乙炔基噻吩）。FLP TMP ···（C 6 F 5）3，t- Bu 3 P···B（C 6 F 5）3和Lut ···（C 6 F 5）3与乙炔（HC≡CH）反应生成明显热力学更稳定的E异构体[ TMP H] [（C 6 F 5）2 B-C（C 6 F 5）═C（H）B（C 6 F 5）3 ]（1- E），t- Bu 3 PC（H）═C（H）B（C 6 F 5）3（2- E ; 90％）和[ t- Bu 3 PH] [（C 6 F 5）2 B-C（C 6 F 5）═C（H）B（C 6 F 5）3 ]（3- E ; 10％）和Lut C（H）═C（H）B（C 6 F 5）3（4- E） 。乙炔反应的机械途径建议从形成弱的B（C
• Facile synthesis of electrophilic vinyl boranes: reactions of alkynyl-borates and diazonium salts
  作者：Xiaoxi Zhao、Liyuan Liang、Douglas W. Stephan

  DOI：10.1039/c2cc35553a

  日期：——

  Reactions of alkynylborate salts, easily derived from reaction of frustrated Lewis pairs with terminal alkynes, with diazonium salts to induce 1,1-carboboration affording a facile and efficient route to substituted electrophilic vinyl boranes.

  炔基硼酸盐与重氮盐的反应很容易从沮丧的路易斯对与末端炔烃反应中衍生出来，与重氮盐诱导1,1-碳硼化反应，从而为取代的亲电子乙烯基硼烷提供了一种简便而有效的途径。
• Dureen, Meghan A.; Stephan, Douglas W., Journal of the American Chemical Society, 2009, vol. 131, p. 8396 - 8397
  作者：Dureen, Meghan A.、Stephan, Douglas W.

  DOI：——

  日期：——