[tBu3PSPh][PhSB(C6F5)3] | 1191247-95-6

• 英文名称: [tBu3PSPh][PhSB(C6F5)3]
• CAS: 1191247-95-6
• 化学式: C₁₈H₃₂PS*C₂₄H₅BF₁₅S
• 分子量: 932.649
• InChiKey: ATVPJWZLDGUCFN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [tBu3PSPh][PhSB(C6F5)3] 、 三苯碳四(五氟苯基)硼酸盐 以 二氯甲烷 为溶剂， 以79%的产率得到[tBu3PSPh][B(C6F5)4]
  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：

  三叔丁基膦 以 甲苯 为溶剂， 生成 [tBu3PSPh][PhSB(C6F5)3]
  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

文献信息

• Activation of Alkyl C–F Bonds by B(C₆F₅)₃: Stoichiometric and Catalytic Transformations
  作者：Christopher B. Caputo、Douglas W. Stephan

  DOI：10.1021/om200885c

  日期：2012.1.9

  The Lewis acid B(C6F5)3 is shown to activate a series of alkyl fluorides. In stoichiometric reactions, treatment of sterically demanding phosphines with B(C6F5)3/alkyl fluorides gives phosphonium fluoroborate salts while treatment of B(C6F5)3/alkyl fluorides with the salts [tBu3PX][XB(C6F5)3] (X = H, PhS) gives the alkane and the salt byproduct [tBu3PX][FB(C6F5)3]. These fluoroalkanes are also catalytically

  显示路易斯酸B（C 6 F 5）3活化一系列烷基氟化物。在化学计量反应中，用B（C 6 F 5）3 /烷基氟化物处理空间要求的膦，得到氟硼酸phospho盐，而用盐[ t Bu 3 PX] [XB]处理B（C 6 F 5）3 /烷基氟化物。（C 6 F 5）3 ]（X = H，PhS）得到烷烃和盐副产物[ t Bu 3 PX] [FB（C 6 F 5）3]。通过使用B（C 6 F 5）3作为催化剂，通过氟代烷烃与Et 3 SiH的反应，这些氟代烷烃也被催化转化为相应的烷烃。