Triphenylphosphonium-methylentriphenylphosphoran-chlorid | 58513-98-7

• 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: Triphenylphosphonium-methylentriphenylphosphoran-chlorid
• 英文别名: Triphenyl[(triphenyl-lambda~5~-phosphanylidene)methyl]phosphanium chloride；triphenyl-[(triphenyl-λ5-phosphanylidene)methyl]phosphanium;chloride
• CAS: 58513-98-7
• 化学式: C₃₇H₃₁P₂*Cl
• 分子量: 573.054
• InChiKey: MAGGRVFSZRZCCM-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  3.74
• 重原子数：
  40
• 可旋转键数：
  7
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  Triphenylphosphonium-methylentriphenylphosphoran-chlorid 、 (dicyclohexylamino)dichlorophosphine 以 苯 为溶剂， 以81%的产率得到
  参考文献：
  名称：

  Preparation, Structural Analysis, and Reactivity Studies of Phosphenium Dications

  摘要：

  This work expands on the recent synthesis and reactivity of the two-coordinate P(III)-containing dication [((Ph3P)(2)C)P((NPr2)-Pr-i)](2+) (3a(2+)). Two additional dications of general formula [((RPh2P)(2)C)P(NR2')](2+) (3b(2+), R = 1/2 (CH2)(3), R' = Pr-i; 3c(2+), R = Ph, R' = Cy) have been prepared. Solution and solid-state P-31 NMR isotropic shifts for this dication class were observed around 360 ppm. Except for [3a] [SbF6](2), the P-31 CP/MAS NMR spectra reveal a high degree of structural disorder around the dicationic site in the solid state. Surprisingly, the synthesis of dication 3a(2+) was only possible in the presence of AlCl4-, SbF6-, and substituted tetraarylborates, while the use of ClO4-, OTf-, BF4-, PF6-, and BPh4- resulted in complex product mixtures. Single-crystal X-ray analysis of dications 3a(2+) and 3c(2+) suggested a 4 pi allyllike structure for the central CPN fragment, and this has been supported through detailed theoretical investigations. Initial reactivity studies between dications 3a(2+)/3c(2+) and PMe3 show an equilibrium between the free dication and the target adduct. Furthermore, 3a(2+) has been shown to be capable of O-H bond activation using water and methanol and polymerizes THE when it is dissolved in this solvent.

  DOI：

  10.1021/acs.organomet.5b00763
• 作为产物：
  描述：

  在 盐酸 作用下， 以 乙醚 为溶剂， 生成 Triphenylphosphonium-methylentriphenylphosphoran-chlorid 、 5-(Ethoxycarbonylmethyl-amino)-2-mercapto-thiazole-4-carboxylic acid ethyl ester
  参考文献：
  名称：

  Bestmann, Hans Juergen; Oechsner, Helmut, Zeitschrift fur Naturforschung, Teil B: Anorganische Chemie, Organische Chemie, 1983, vol. 38, # 7, p. 861 - 865

  摘要：

  DOI：

文献信息

• US3957978A
  申请人：——

  公开号：US3957978A

  公开（公告）日：1976-05-18
• Bestmann, Hans Juergen; Oechsner, Helmut, Zeitschrift fur Naturforschung, Teil B: Anorganische Chemie, Organische Chemie, 1983, vol. 38, # 7, p. 861 - 865
  作者：Bestmann, Hans Juergen、Oechsner, Helmut

  DOI：——

  日期：——
• Preparation, Structural Analysis, and Reactivity Studies of Phosphenium Dications
  作者：Madelyn Qin Yi Tay、Gordana Ilić、Ulrike Werner-Zwanziger、Yunpeng Lu、Rakesh Ganguly、Louis Ricard、Gilles Frison、Duncan Carmichael、Dragoslav Vidović

  DOI：10.1021/acs.organomet.5b00763

  日期：2016.2.22

  This work expands on the recent synthesis and reactivity of the two-coordinate P(III)-containing dication [((Ph3P)(2)C)P((NPr2)-Pr-i)](2+) (3a(2+)). Two additional dications of general formula [((RPh2P)(2)C)P(NR2')](2+) (3b(2+), R = 1/2 (CH2)(3), R' = Pr-i; 3c(2+), R = Ph, R' = Cy) have been prepared. Solution and solid-state P-31 NMR isotropic shifts for this dication class were observed around 360 ppm. Except for [3a] [SbF6](2), the P-31 CP/MAS NMR spectra reveal a high degree of structural disorder around the dicationic site in the solid state. Surprisingly, the synthesis of dication 3a(2+) was only possible in the presence of AlCl4-, SbF6-, and substituted tetraarylborates, while the use of ClO4-, OTf-, BF4-, PF6-, and BPh4- resulted in complex product mixtures. Single-crystal X-ray analysis of dications 3a(2+) and 3c(2+) suggested a 4 pi allyllike structure for the central CPN fragment, and this has been supported through detailed theoretical investigations. Initial reactivity studies between dications 3a(2+)/3c(2+) and PMe3 show an equilibrium between the free dication and the target adduct. Furthermore, 3a(2+) has been shown to be capable of O-H bond activation using water and methanol and polymerizes THE when it is dissolved in this solvent.