bis(di-tert-butyl(methyl)-l5-phosphaneyl)(vinylidene)ruthenium(VI) chloride hydride | 203192-11-4

• 英文名称: bis(di-tert-butyl(methyl)-l5-phosphaneyl)(vinylidene)ruthenium(VI) chloride hydride
• CAS: 203192-11-4
• 化学式: C₂₀H₄₅ClP₂Ru
• 分子量: 484.048
• InChiKey: OTDIBOQFGAOQNB-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为产物：
  描述：

  chloro(trihydrido)ruthenium;ditert-butyl(methyl)phosphane 、 乙炔 以 甲苯 为溶剂， 以76%的产率得到bis(di-tert-butyl(methyl)-l5-phosphaneyl)(vinylidene)ruthenium(VI) chloride hydride
  参考文献：
  名称：

  Isomeric Hydrido/Vinylidene, MH(halide)(CCH₂)L₂, and Ethylidyne, M(halide)(C−CH₃)L₂ (M = Os, Ru; L = Phosphine), Are Energetically Similar but Not Interconverting

  摘要：

  It is shown that there is no deuterium-isotope incorporation in the vinylidene CHPh group of RuDX(CCHPh)((PBu2Me)-Bu-t)(2) (X = Cl, I) on the time scale of 24 h at 25 degrees C, which indicates that the (unobserved) isomeric alkylidyne species RuX(CCHDPh)((PBu2Me)-Bu-t)(2) is not readily accessible under these conditions. Ab initio (B3LYP) calculations on the model MHCl(CCH2)(PH3)(2) (M = OS, Ru) show the ethylidyne isomer MCl(CCH3)(PH3)(2) to be close in energy (2.5, -1.1 kcal mol(-1) for Os and Ru, respectively) and effectively inaccessible at 25 degrees C due to the high energy (54.2, 45.5 kcal mol(-1) for Os and Ru, respectively) of the transition state for such a 1,3-migration. In contrast, simple rotation of the CCH2 group of MHCl(CCH2)(PH3)(2) by 180 degrees around the C-C axis is calculated to have a low barrier (8.1, 4.3 kcal mol(-1) for Os and Ru, respectively), indicating this to be the mechanism for isomerization observed in OsHCl(CCHPh)((PPr3)-Pr-i)(2).

  DOI：

  10.1021/om9709493