[tBu3PS(p-tolyl)][(p-tolylS)B(C6F5)3] | 1191247-99-0

• 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: [tBu3PS(p-tolyl)][(p-tolylS)B(C6F5)3]
• 英文别名: (4-Methylphenyl)sulfanyl-tris(2,3,4,5,6-pentafluorophenyl)boranuide;tritert-butyl-(4-methylphenyl)sulfanylphosphanium
• CAS: 1191247-99-0
• 化学式: C₁₉H₃₄PS*C₂₅H₇BF₁₅S
• 分子量: 960.702
• InChiKey: GLHQBTYACGMCQT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  14.26
• 重原子数：
  63
• 可旋转键数：
  10
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  50.6
• 氢给体数：
  0
• 氢受体数：
  18

反应信息

• 作为反应物：
  描述：

  [tBu3PS(p-tolyl)][(p-tolylS)B(C6F5)3] 以 二氯甲烷 为溶剂， 生成 [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：

  对甲苯二硫醚 、 [tBu3PSPh][PhSB(C6F5)3] 以 not given 为溶剂， 生成 [tBu3PS(p-tolyl)][(p-tolylS)B(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