[(1,1,1-tris-(diphenylphosphinomethyl)ethane)Ru(η²-OAc)Cl] | 1003045-51-9

• 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: [(1,1,1-tris-(diphenylphosphinomethyl)ethane)Ru(η²-OAc)Cl]
• 英文别名: [(Triphos)Ru(η²-OAc)Cl]；[RuCl(κ3-triphos)(CH3Co2)]；[3-diphenylphosphanyl-2-(diphenylphosphanylmethyl)-2-methylpropyl]-diphenylphosphane;ruthenium(2+);acetate;chloride
• CAS: 1003045-51-9
• 化学式: C₄₃H₄₂ClO₂P₃Ru
• 分子量: 820.25
• InChiKey: MOPAOIRSMYTLCK-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  4.15
• 重原子数：
  50
• 可旋转键数：
  6
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  40.1
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  盐酸 、 [(1,1,1-tris-(diphenylphosphinomethyl)ethane)Ru(η²-OAc)Cl] 以 盐酸 、 二氯甲烷 为溶剂， 以81%的产率得到[tris(μ-chloro)bis((triphos)ruthenium(II))] chloride
  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：

  三乙胺盐酸盐 、 [RuH(OAc-κ2O,O’)(triphos)] 以 二氯甲烷-D2 为溶剂， 生成 [(1,1,1-tris-(diphenylphosphinomethyl)ethane)Ru(η²-OAc)Cl]
  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：

  1-(3,4-二甲氧基苯基)-2-(2-甲氧基苯基)-丙烷-1,3-二醇 在 [(1,1,1-tris-(diphenylphosphinomethyl)ethane)Ru(η²-OAc)Cl] 作用下， 以 5,5-dimethyl-1,3-cyclohexadiene 为溶剂， 反应 4.0h， 以5%的产率得到木榴油
  参考文献：
  名称：

  钌催化的C ？木质素模型基质中的C键裂解

  摘要：

  钌-三膦络合物氧化还原中性Ç表现出前所未有的催化活性和选择性的β-O-4木质素1,3- dilignol模型化合物键的C键断裂。根据实验数据和DFT计算，提出了一种涉及脱氢引发的逆式羟醛反应进行CC键断裂的机理。

  DOI：

  10.1002/anie.201410620

文献信息

• Hydrogenation of carbon dioxide to methanol using a homogeneous ruthenium–Triphos catalyst: from mechanistic investigations to multiphase catalysis
  作者：Sebastian Wesselbaum、Verena Moha、Markus Meuresch、Sandra Brosinski、Katharina M. Thenert、Jens Kothe、Thorsten vom Stein、Ulli Englert、Markus Hölscher、Jürgen Klankermayer、Walter Leitner

  DOI：10.1039/c4sc02087a

  日期：——

  identified as the key intermediate, leading to the synthesis of the analogous acetate complex as a robust and stable precursor for the catalytic transformation. A detailed mechanistic study using DFT calculations shows that a sequential series of hydride transfer and protonolysis steps can account for the transformation of CO2via formate/formic acid to hydroxymethanolate/formaldehyde and finally methanolate/methanol

  CO 2氢化成甲醇可以使用单分子有机金属催化剂来实现。虽然以前认为均相催化剂仅允许通过甲酸酯作为稳定的中间体进行氢化，但目前的机理研究表明，多步转化可以直接在 Ru-Triphos（Triphos = 1,1,1-三（二苯基膦甲基）乙烷）上发生中心。阳离子甲酸盐络合物 [(Triphos)Ru(η 2 -O 2 CH)(S)] +（S = 溶剂）被确定为关键中间体，导致合成类似的乙酸盐络合物作为催化转化的稳健和稳定的前体。使用 DFT 计算的详细机理研究表明，一系列连续的氢化物转移和质子分解步骤可以解释 CO 2通过甲酸盐/甲酸转化为羟基甲醇化物/甲醛，最后在单个 Ru-Triphos 的配位范围内转化为甲醇化物/甲醇-分段。系统参数优化的所有实验结果与该机理图完全一致。基于这些发现，一个由 H 2组成的双相系统开发了 O 和 2-MTHF，其中活性阳离子钌络合物存在于有机相中以供循环使用，甲醇用水相萃取。