| 203179-08-2

• CAS: 203179-08-2
• 化学式: C₂₁H₄₈Cl₂OsP₂
• 分子量: 623.666
• InChiKey: XDIDDQRBICEBJF-UHFFFAOYSA-L

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

• 作为反应物：
  描述：

  、 一氧化碳 以 二氯甲烷-D2 为溶剂， 生成
  参考文献：
  名称：

  Osmium Converts Terminal Olefins to Carbynes:  α-Hydrogen Migration Redox Isomers with Reversed Stability for Ruthenium and for Osmium

  摘要：

  Os(H)(2)Cl2L2 (L = (PPr3)-Pr-i) reacts with propylene or styrene to give equimolar amounts of OsHCl2(CCH2R)L-2 and the hydrogenated olefin; these molecules are isomeric with the ruthenium carbenes RuCl2[C(H)CH2R]L-2, yet these distinct redox alternatives are thermodynamically preferred. Ab initio (B3LYP) calculations show that the unsaturated five-coordinate MCl2(CHMe)(PH3)(2) is more stable than the saturated hexacoordinate MCl2H(CMe)(PH3)(2) for M = Ru, while the two species are almost isoenergetic in the case of Os; computationally, it is found that the osmium hydride carbyne involves a large activation energy (27.2 kcal/mol) to transform unimolecularly to its carbene isomer.

  DOI：

  10.1021/om9711382
• 作为产物：
  描述：

  三聚丙烯 、 bis(triisopropylphosphane)(dihydrido)dichloroosmium(IV) 以 甲苯 为溶剂， 以100%的产率得到
  参考文献：
  名称：

  Osmium Converts Terminal Olefins to Carbynes:  α-Hydrogen Migration Redox Isomers with Reversed Stability for Ruthenium and for Osmium

  摘要：

  Os(H)(2)Cl2L2 (L = (PPr3)-Pr-i) reacts with propylene or styrene to give equimolar amounts of OsHCl2(CCH2R)L-2 and the hydrogenated olefin; these molecules are isomeric with the ruthenium carbenes RuCl2[C(H)CH2R]L-2, yet these distinct redox alternatives are thermodynamically preferred. Ab initio (B3LYP) calculations show that the unsaturated five-coordinate MCl2(CHMe)(PH3)(2) is more stable than the saturated hexacoordinate MCl2H(CMe)(PH3)(2) for M = Ru, while the two species are almost isoenergetic in the case of Os; computationally, it is found that the osmium hydride carbyne involves a large activation energy (27.2 kcal/mol) to transform unimolecularly to its carbene isomer.

  DOI：

  10.1021/om9711382

文献信息

• Hydrogen Migration and HCl Elimination Promoted by Metal-Centered Nucleophilic Attack on Osmium Hydrido−Carbynes
  作者：Greg J. Spivak、Kenneth G. Caulton

  DOI：10.1021/om980597f

  日期：1998.11.1

  The carbynes [OsHCl2(CCH2R)L-2] (R=Ph, CH3; L=(PPr3)-Pr-i) react with CO to give, after 1,2-hydride migration from osmium to C-alpha of the carbyne ligand, the osmium carbene complexes [OsCl2(CO)(=CHCH2R)L-2]. For R=Ph, reactions with excess CO lead to HCl elimination to form. [OsCl(CO)(2)((E)-CH=CHPh)L-2], which reacts with liberated HCl at C-alpha to yield [OsCl2(CO)(2)L-2] and CH2=CHPh. Abstraction of chloride from either the carbynes or carbenes with NaBAr4' (Ar'=3,5-C6H3(CF3)(2)) yields the corresponding coordinatively unsaturated carbyne and carbene complexes [OsHCl(CCH2R)L-2][BAr'(4)] and [OsCl(CO)(=CHCH2R)L-2][BAr'(4)], respectively. The carbynes [OsHCl(CCH2Ph)L-2](+) react with reagent L'(L'=CO, HCCR') to initially give the carbenes [OsCl(L')(=CHCH2Ph)L-2](+) after 1,2-hydride migration to C-alpha of the carbyne ligand. These carbenes react further, eliminating HCl and undergoing selective protonation to yield either [OsCl(CO)(3)L-2](+) and CH2=CHPh (with L'=CO) or the sigma-vinyl carbyne complexes [OsCl(CCH2R')((E)-CH=CHPh)L-2](+) (with L'=HCCR').