Dibromotungsten;trimethylphosphane | 159224-52-9

• 分子结构分类: 有机化合物 - 有机磷化合物
• 英文名称: Dibromotungsten;trimethylphosphane
• CAS: 159224-52-9；163381-62-2
• 化学式: C₁₂H₃₆Br₂P₄W
• 分子量: 647.971
• InChiKey: GRIZVCODZZFLDO-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  7.12
• 重原子数：
  19
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 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：

  Dibromotungsten;trimethylphosphane 、 烯丙基三甲基硅烷 在 ferrocene 作用下， 以 氘代苯 为溶剂， 以90%的产率得到
  参考文献：
  名称：

  Formation of tungsten carbyne complexes from vinyl- and allyssilanes and -stannanes

  摘要：

  WX(2)(PMe(3))(4) [X = Cl (1a), Br (1b)] react with the vinyl reagents CH2=CHR [R = SiMe(3), Si(OEt)Me(2), Si(OMe)(3) and Sn(n)Bu(3)] to give the tungsten methylcarbyne plexes W(=CCH3)X(PMe(3))(4) [X = Cl (2a), Br (2b)] and XSiR(3) and XSnR(3). The connectivity of 2a has been confirmed by NMR and an X-ray crystal structure. Similarly, the allyl reagents CH2=CHCH(2)R [R = SiMe(3), SiClMe(2), Si(OMe)(3) and SnMe(3)] react with la and 1b to give the ethyl carbynes W(=CCH2CH3)X(PMe(3))(4) [X = Cl (6a), Br (6b)]. Reactions of (CH2)-C-13=CHSiMe(3) and CH2-CDSiMe(3) show that the methylcarbyne ligand is formed by net migration of the methyne hydrogen to the methylene carbon, but a crossover experiment with both of these substrates shows that the rearrangement is not intramolecular. In some of the reactions, pre-equilibrium formation of a tungsten(II) vinylsilane complex is observed. The proposed mechanism for carbyne formation, based on kinetic and labeling studies, involves loss of XSiR, from the vinylsilane intermediate to give a tungsten vinyl species. The vinyl complex is deprotonated to a vinylidene which is reprotonated to the carbyne. The relative rates of carbyne formation span more than three orders of magnitude, with reactions of 1a faster than 1b and CH2=CHSn(n)Bu(3) > CH2=CH CH(2)SnMe(3) > CH2=CHSi(OMe)(3) > CH2=CHSiMe(3) > CH2=CHCH2Si(OMe)(3) > CH2=CHCH(2)SiMe(3). A primary determinant of relative reactivity is the initial binding of the olefinic substrate to tungsten(II).

  DOI：

  10.1016/0277-5387(94)00356-j
• 作为产物：
  描述：

  WCl2(PMe3)4 、 lithium bromide 以 四氢呋喃 为溶剂， 以39%的产率得到Dibromotungsten;trimethylphosphane
  参考文献：
  名称：

  Formation of tungsten carbyne complexes from vinyl- and allyssilanes and -stannanes

  摘要：

  WX(2)(PMe(3))(4) [X = Cl (1a), Br (1b)] react with the vinyl reagents CH2=CHR [R = SiMe(3), Si(OEt)Me(2), Si(OMe)(3) and Sn(n)Bu(3)] to give the tungsten methylcarbyne plexes W(=CCH3)X(PMe(3))(4) [X = Cl (2a), Br (2b)] and XSiR(3) and XSnR(3). The connectivity of 2a has been confirmed by NMR and an X-ray crystal structure. Similarly, the allyl reagents CH2=CHCH(2)R [R = SiMe(3), SiClMe(2), Si(OMe)(3) and SnMe(3)] react with la and 1b to give the ethyl carbynes W(=CCH2CH3)X(PMe(3))(4) [X = Cl (6a), Br (6b)]. Reactions of (CH2)-C-13=CHSiMe(3) and CH2-CDSiMe(3) show that the methylcarbyne ligand is formed by net migration of the methyne hydrogen to the methylene carbon, but a crossover experiment with both of these substrates shows that the rearrangement is not intramolecular. In some of the reactions, pre-equilibrium formation of a tungsten(II) vinylsilane complex is observed. The proposed mechanism for carbyne formation, based on kinetic and labeling studies, involves loss of XSiR, from the vinylsilane intermediate to give a tungsten vinyl species. The vinyl complex is deprotonated to a vinylidene which is reprotonated to the carbyne. The relative rates of carbyne formation span more than three orders of magnitude, with reactions of 1a faster than 1b and CH2=CHSn(n)Bu(3) > CH2=CH CH(2)SnMe(3) > CH2=CHSi(OMe)(3) > CH2=CHSiMe(3) > CH2=CHCH2Si(OMe)(3) > CH2=CHCH(2)SiMe(3). A primary determinant of relative reactivity is the initial binding of the olefinic substrate to tungsten(II).

  DOI：

  10.1016/0277-5387(94)00356-j