[RuH(OAc-κ2O,O’)(triphos)] | 1003045-52-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [RuH(OAc-κ2O,O’)(triphos)]
• 英文别名: [RuH(OAc-κ²O,O’)(triphos)]；[RuH(acetate)(κ3-1,1,1-tris(diphenylphosphinomethyl)ethane)]；[RuH(OAc)(κ3-triphos)]
• CAS: 1003045-52-0
• 化学式: C₄₃H₄₃O₂P₃Ru
• 分子量: 785.804
• InChiKey: BUTPUUXZMFCZME-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

• 作为反应物：
  描述：

  苯乙烯 、 [RuH(OAc-κ2O,O’)(triphos)] 以 二氯甲烷-D2 为溶剂， 生成 [Ru(CH2CH2Ph)(OAc)(κ3-triphos)]
  参考文献：
  名称：

  Reactivity and Catalytic Activity of a Robust Ruthenium(II)−Triphos Complex

  摘要：

  The ruthenium(II)-triphos acetatc, complex [RuCl(OAc)(k(3)-triphos)] (triphos = (PPh2CH2)(3)CMe) has been found to be an active catalyst precursor for the hydrogenation of 1-alkenes under relatively mild conditions (5-50 bar H-2, 50 degrees C). In contrast to related triphenylphosphine complexes, [RuCl(OAc)(k(3)-triphos)] is much less air sensitive and 14 high catalytic activities were achieved when catalyst samples were prepared without exclusion of air or moisture. Substitution of the acetatc, ligand can be effected by treatment of acid, affording [Ru-2(mu-Cl)(3)(k(3)-triphos)(2)]Cl and [RuCl(k(3)-triphos)](2)(BF4)(2) with aqueous HCl and [Et2OH]BF4, respectively, or by heating with dmpm in the presence of [NH4]PF6, resulting in formation of [RuCl(k(2)-dMPM)(k(3)-triphos)]PF6 (dmpm = PMe(2)CH(2)PMe2). A hydride complex, [RuHCl (k(3)-triphos)], formed by acetato-mediated heterolytic cleavage of dihydrogen is proposed as the active catalytic species. An inner-sphere, monohydride mechanism is suggested for the catalytic cycle, with chloro and triphos ligands playing a spectator role. These mechanistic proposals are consistent with reactivity studies carried out on [RuCl(OAc) (k(3)-triphos)] and [RuH(OAc)(k(3)-triphos)] and supported by a computational analysis. The solid-state structures of [RuCl(OAc)(k(3)-triphos)], [RuCl(k(3)-triphos)](2)(BF4)(2), and [RUCl(k(2)-dmpm)(k(3)-triphos)]PF6 have been established by X-ray diffraction.

  DOI：

  10.1021/ic701773a
• 作为产物：
  描述：

  氢气 、 [(1,1,1-tris-(diphenylphosphinomethyl)ethane)Ru(η²-OAc)Cl] 在 Et₃N 作用下， 以 二氯甲烷-D2 为溶剂， 生成 [RuH(OAc-κ2O,O’)(triphos)]
  参考文献：
  名称：

  Reactivity and Catalytic Activity of a Robust Ruthenium(II)−Triphos Complex

  摘要：

  The ruthenium(II)-triphos acetatc, complex [RuCl(OAc)(k(3)-triphos)] (triphos = (PPh2CH2)(3)CMe) has been found to be an active catalyst precursor for the hydrogenation of 1-alkenes under relatively mild conditions (5-50 bar H-2, 50 degrees C). In contrast to related triphenylphosphine complexes, [RuCl(OAc)(k(3)-triphos)] is much less air sensitive and 14 high catalytic activities were achieved when catalyst samples were prepared without exclusion of air or moisture. Substitution of the acetatc, ligand can be effected by treatment of acid, affording [Ru-2(mu-Cl)(3)(k(3)-triphos)(2)]Cl and [RuCl(k(3)-triphos)](2)(BF4)(2) with aqueous HCl and [Et2OH]BF4, respectively, or by heating with dmpm in the presence of [NH4]PF6, resulting in formation of [RuCl(k(2)-dMPM)(k(3)-triphos)]PF6 (dmpm = PMe(2)CH(2)PMe2). A hydride complex, [RuHCl (k(3)-triphos)], formed by acetato-mediated heterolytic cleavage of dihydrogen is proposed as the active catalytic species. An inner-sphere, monohydride mechanism is suggested for the catalytic cycle, with chloro and triphos ligands playing a spectator role. These mechanistic proposals are consistent with reactivity studies carried out on [RuCl(OAc) (k(3)-triphos)] and [RuH(OAc)(k(3)-triphos)] and supported by a computational analysis. The solid-state structures of [RuCl(OAc)(k(3)-triphos)], [RuCl(k(3)-triphos)](2)(BF4)(2), and [RUCl(k(2)-dmpm)(k(3)-triphos)]PF6 have been established by X-ray diffraction.

  DOI：

  10.1021/ic701773a
• 作为试剂：
  描述：

  N-乙酰苯胺 在 [RuH(OAc-κ2O,O’)(triphos)] 、 氢气 作用下， 以 四氢呋喃 为溶剂， 210.0 ℃ 、1.0 MPa 条件下， 反应 16.0h， 生成 乙醇 、 N-乙基苯胺 、 N,N-二乙基苯胺
  参考文献：
  名称：

  酰胺的均相催化加氢为胺

  摘要：

  在[Ru（acac）3 ]（acacH = 2,4-戊二酮），三[[1,1,1-三（二苯基膦甲基）乙烷]]和甲磺酸（MSA）的存在下进行酰胺加氢生成仲胺和叔胺如果在N上至少有一个芳环，则其选择性高达93％。该系统对伯胺的合成也具有活性。为了探索MSA的作用和反应机理，已经从[Ru（acac）3 ]，三醇和MSA或[RuX（OAc）（triphos）]的反应中制备了一系列甲磺酸钠络合物。 （X = H或OAc）或[RuH 2（CO）（triphos ）]与MSA。晶体学表征复合物包括：[茹（OAC-κ 1 O）2（H 2O）（triphos）]，[Ru（OAc‐κ 2 O，O'）（CH 3 SO 3 ‐κ 1 O）（triphos ）]，[Ru（CH 3 SO 3‐ κ 1 O）2（H 2 O）（三膦）]和[孺2（μ-CH 3 SO 3）3（三磷酸）2 ] [CH 3 SO 3 ]，而其他复合物，例如[茹（OAC-κ

  DOI：

  10.1002/chem.201204270