Triphenyl-{phenyl-[phenyl-(triphenyl-λ5-phosphanylidene)-methylphosphanylidene]-methyl}-phosphonium; chloride | 140199-81-1

• 英文名称: Triphenyl-{phenyl-[phenyl-(triphenyl-λ5-phosphanylidene)-methylphosphanylidene]-methyl}-phosphonium; chloride
• CAS: 140199-81-1
• 化学式: C₅₀H₄₀P₃*Cl
• 分子量: 769.242
• InChiKey: VUDQOARACGSKTF-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  7.28
• 重原子数：
  54.0
• 可旋转键数：
  10.0
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  Triphenyl-{phenyl-[phenyl-(triphenyl-λ5-phosphanylidene)-methylphosphanylidene]-methyl}-phosphonium; chloride 在 磺酰氯 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以100%的产率得到
  参考文献：
  名称：

  Bis(ylide)-substituted phosphenium and phosphonium halides

  摘要：

  The bis(triphenylphosphoniumyldyl)halophosphines expected from the condensation of ylidyl dihalophosphines with trimethylsilyl ylides or of their addition to carbodiphosphoranes enter a spontaneous dissociation to yield bis(ylidyl)phosphenium halides. They are the first phosphenium salts which do not need anions of low basicity such as AlCl4-. P-31 NMR spectra and, in one case, a single-crystal X-ray investigation reveal an essentially planar structure of the PCPCP skeleton with E,E-conformation. The bis(ylidyl)phosphenium halides are protonated at an ylidic carbon atom while at the same time the halide ion is re-associated to the central phosphorus atom. They add halogen or ortho quinones to the central phosphorus to yield the corresponding phosphonium ions. They are also oxidized by elemental sulfur or gray selenium resulting in bis(ylidyl)thio- and -seleno-phosphinyl halides. As can be shown by their solvent dependent P-31 NMR spectra, they dissociate in polar media to yield the first examples of chalcogenoxophosphonium halides. As revealed by another X-ray structure analysis, the conjugation in a bis(ylidyl)dihalophosphonium ion is interrupted at the central phosphorus atom.

  DOI：

  10.1016/s0022-328x(96)06443-1
• 作为产物：
  描述：

  三苯基苄基溴化膦 在 三氯化磷 作用下， 生成 Triphenyl-{phenyl-[phenyl-(triphenyl-λ5-phosphanylidene)-methylphosphanylidene]-methyl}-phosphonium; chloride
  参考文献：
  名称：

  Spontaneous dissociation of phosphoniumylidyl-chlorophosphines to ionic phosphenium chlorides

  摘要：

  The products from the replacement of two chlorofunctions of PCl3 by a pair of phosphoniumylidyl substituents or by both a phosphoniumylidyl and an amino substituent are ionic phosphenium chlorides and not covalent chlorophosphines.

  DOI：

  10.1016/s0040-4039(00)93971-6

文献信息

• Bis(triphenylphosphoniumyIidyl)phosphane
  作者：G. Jochem、A. Schmidpeter、H. Nöth

  DOI：10.1515/znb-1996-0217

  日期：1996.2.1

  Bis(ylidyl)phosphanes can be prepared from ylides and dichlorophosphanes or from bis-(ylidyl)phosphenium chlorides and organolithium compounds. By substituting in bis(ylidyl)-phosphenium chlorides the chloride ion for more basic anions, a large variety of bis(ylidyl)-phosphanes is accessible. They can be protonated at the ylidic carbon atoms, but alkylated and oxidized at the central phosphorus atom. As shown by ³¹P NM R in solution and by X-ray investigation of the crystal, the lone pair at the tervalent phosphorus is generally oriented synperiplanar to both phosphonio groups.

  《摘要》 Bis(ylidyl)磷烷可以通过亚胺和二氯化磷或双(亚胺基)磷氯化物与有机锂化合物制备。通过在双(亚胺基)磷氯化物中用更基本的阴离子替代氯离子，可以获得各种各样的双(亚胺基)磷烷。它们可以在亚胺基碳原子上质子化，但可以在中心磷原子上烷基化和氧化。通过溶液中的31P NMR和晶体的X射线研究表明，三价磷的孤对电子通常与两个磷离子基团同平面排列。
• Ylide‐Stabilized Phosphenium Cations: Impact of the Substitution Pattern on the Coordination Chemistry
  作者：Tobias Stalder、Felix Krischer、Henning Steinert、Philipp Neigenfind、Viktoria H. Gessner

  DOI：10.1002/chem.202104074

  日期：2022.2.7

  cations is reported. The monoylidyl cations exhibit a distinctly higher reactivity and electrophilicity, thus yielding a chlorophosphine gold cation via chloride shift from gold to phosphorus. In contrast, the diylidyl cation formed the phosphenium AuCl complex, demonstrating the tunability of the phosphenium cation reactivity.

  转换选择性：报道了一系列叶立德取代的鏻阳离子的分离和配位化学。单酰基阳离子表现出明显更高的反应性和亲电性，从而通过氯从金向磷的转变产生氯膦金阳离子。相反，二亚基阳离子形成鏻AuCl络合物，证明了鏻阳离子反应活性的可调性。
• Schmidpeter, Alfred; Jochem, Georg; Thiele, Martin, Phosphorus, Sulfur and Silicon and the Related Elements, 1993, vol. 76, # 1-4, p. 13 - 16
  作者：Schmidpeter, Alfred、Jochem, Georg、Thiele, Martin

  DOI：——

  日期：——
• Schmidpeter, Alfred; Jochem, Georg; Karaghiosoff, Konstantin, Angewandte Chemie, 1992, vol. 104, # 10, p. 1420 - 1421
  作者：Schmidpeter, Alfred、Jochem, Georg、Karaghiosoff, Konstantin、Robl, Christian

  DOI：——

  日期：——
• Jochem, Georg; Karaghiosoff, Konstantin; Robl, Christian, Phosphorus, Sulfur and Silicon and the Related Elements, 1993, vol. 77, # 1-4, p. 233
  作者：Jochem, Georg、Karaghiosoff, Konstantin、Robl, Christian、Schmidpeter, Alfred

  DOI：——

  日期：——