2,3,4,5,2',3',4',5',-octamethylbi-1,1'-phospholyl | 122762-51-0

• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机膦及其衍生物
• 英文名称: 2,3,4,5,2',3',4',5',-octamethylbi-1,1'-phospholyl
• 英文别名: 2,3,4,5,2',3',4',5'-octamethyl-1,1'-bisphospholyl；2,3,4,5,2',3',4',5'-octamethyl-1,1'-biphospholyl；2,3,4,5,2',3',4',5'-octamethylbi-1,1'-phospholyl；2,3,4,5-Tetramethyl-1-(2,3,4,5-tetramethylphosphol-1-yl)phosphole
• CAS: 122762-51-0
• 化学式: C₁₆H₂₄P₂
• 分子量: 278.314
• InChiKey: HMSMPRHSJRXWKD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  18
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  2,3,4,5,2',3',4',5',-octamethylbi-1,1'-phospholyl 在 2-氯苯亚甲基丙二腈 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 以64%的产率得到caesium 2,3,4,5-tetramethylphospholide
  参考文献：
  名称：

  Synthesis of heavier alkali metal phospholides. Crystal structure of caesium 2,3,4,5-tetramethylphospholide, an ionic solid

  摘要：

  The reaction of rubidium or caesium metals with 2,3,4,5,2',3',4',5'-octamethylbi-1,1'-phospholyl (3) in THE respectively, afforded rubidium 2,3,4,5-tetramethylphospholide (1) and caesium 2,3,4,5-tetramethylphospholide (2). While the physical properties of 1 are very similar to that of the already described potassium 2,3,4,5-tetramethylphospholide, in particular as far as solubility is concerned, 2 on the contrary is very slightly soluble even in polar solvents such as dimethoxyethane (DME) or THF. Crystals of 2 suitable for X-ray analysis have been obtained by high-temperature recrystallisation in DME at 170 degreesC. The three-dimensional polymeric structure of 2, where all the phospholyl rings are parallel, has the characteristics of an ionic solid. (C) 2002 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0022-328x(01)01247-5
• 作为产物：
  描述：

  1-chloro-2,3,4,5-tetramethylphosphole 在 氢化镱 、 mercury dichloride 作用下， 以 四氢呋喃 为溶剂， 生成 2,3,4,5,2',3',4',5',-octamethylbi-1,1'-phospholyl
  参考文献：
  名称：

  Phosphorus–heteroatom bond cleavage by ytterbium metal. Synthesis of mono(η⁵-tetramethylphospholyl)ytterbium(II) chloride and thiolate complexes and structural characterisation of [Yb(µ-Cl)(η⁵-C₄Me₄P)(thf)₂]₂and [Yb(µ-SPh)(η⁵-C₄Me₄P)(thf)₂]₂

  摘要：

  结构特征为[Yb(µ-Cl)(µ5-C4Me4P)(thf)2]22和[Yb(µ-SPh)(µ5-C4Me4P)(thf)2]24可通过分别用镱金属在室温下在四氢呋喃中直接裂解1-氯-和1-苯硫基-2,3,4,5-四甲基磷的P-Cl或P-S键轻松制备，而4也可以通过2与NaSPh的反应制备。

  DOI：

  10.1039/c39940002723

文献信息

• Phospholyl (phosphacyclopentadienyl) and arsolyl (arsacyclopentadienyl) complexes of ytterbium(II) and samarium(II). Synthetic, structural and multinuclear (31P and 171Yb) NMR studies
  作者：F. Nief、L. Ricard、F. Mathey

  DOI：10.1016/s0277-5387(00)87048-5

  日期：1993.1

  Bis(eta5-phospholyl) or bis(eta5-arsolyl)M(THF)2 complexes, where M = Sm or Yb, can be obtained either by reaction of potassium phospholides or arsolides with MI2(THF)2 or by cleavage of the P-P or As-As bond of a biphospholyl or biarsolyl by ytterbium or samarium metal powders. The THF molecules that coordinate to the metal are labile when the ligands are 2,3,4,5-tetramethylphospholyl or arsolyl, but not when they are 2,5-diphenylphospholyl. An X-ray crystal structure of bis(eta5-2,5-diphenylphospholyl)Yb (THF)2 is Presented. Yb-171 and P-31 NMR studies reveal that exchange of ligands is occurring in bis(eta5-2,3,4,5-tetramethylphospholyl)Yb(THF)2; this exchange is slow at room temperature and frozen at -20-degrees-C. For bis(eta5-2,5-phenyldiphenylphospholyl)Yb(THF)2 P-31 NMR data suggest that no exchange is occurring at room temperature.
• Douglas, Trevor; Theopold, Klaus H., Angewandte Chemie, 1989, vol. 101, # 10, p. 1394 - 1395
  作者：Douglas, Trevor、Theopold, Klaus H.

  DOI：——

  日期：——
• Synthesis and Molecular Structure of Bis(pentamethylcyclopentadienyl) Phospholyl- and Arsolylsamarium(III) Complexes: Influence of Steric and Electronic Factors
  作者：François Nief、Louis Ricard

  DOI：10.1021/om010317n

  日期：2001.9.1

  The title complexes could be easily synthesized respectively from the following biphospholyls: 2,3,4,5,2 ' ,3 ' ,4 ' ,5 ' -octamethylbi-1,1 ' -phospholyl (1); 3,4,3 ' ,4 ' -tetramethylbi-1,1 ' -phospholyl (2); 2,5,2 ' ,5 ' -tetra-tert-butylbi-1,1 ' -phospholyl (3), and CP*Sm-2 or Cp*Sm-2(Et2O) (Cp* = pentamethylcyclopentadienyl). 3,4,3 ' ,4 ' -Tetramethylbi-1,1 ' -arsolyl (4), a precursor of the new 3,4-dimethylarsolyl ligand, was prepared in three steps from the known 1-chloro-2,5-di(trimethylsilyl)-3,4-dimethylarsole (5). The reaction of 4 with CP*Sm-2 afforded the title complex 12. Although the unsubstituted bi-1,1 ' -phospholyl could be observed by NMR, it decomposed during the isolation, and thus the title complex 13 with the unsubstituted phospholyl was prepared from Cp*Sm-2(Et2O) and the new thallium phospholide 8, synthesized by metathesis of lithium phospholide with thallous ethoxide. Compounds 8-13 were characterized by X-ray crystallography. The solid state structures of complexes 9-13 vary depending on the substitution pattern on the phospholyl ligand. They can be eta (1)- or eta (5)-coordinated monomers (respectively 9 and 12), a mu:eta (1):eta (5)- symmetrical dimer (13), or even unsymmetrical dimers where both the eta (1)- and the mu:eta (1),eta (5)-coordination modes are found (10 and 11). These structures are discussed by taking into account the electronic and steric properties of the phospholyl and arsolyl ligands.