[[2,5-Ph2-3,4-Tol2-(η4-C4CO)]Ru(CO)2]2 | 954118-81-1

• 英文名称: [[2,5-Ph2-3,4-Tol2-(η4-C4CO)]Ru(CO)2]2
• 英文别名: [2,5-Ph2-3,4-Tol2(η4-C4CO)Ru(CO)2]2
• CAS: 954118-81-1
• 化学式: C₆₆H₄₈O₆Ru₂
• 分子量: 1139.24
• InChiKey: AGWGLWSPMVPGAG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• 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：

  [[2,5-Ph2-3,4-Tol2-(η4-C4CO)]Ru(CO)2]2 、 苯胺 以 二氯甲烷-D2 为溶剂， 生成 [2,5-Ph2-3,4-Tol2(η4-C4CO)](CO)2Ru(aniline)
  参考文献：
  名称：

  Reduction of Imines by Hydroxycyclopentadienyl Ruthenium Hydride:  Intramolecular Trapping Evidence for Hydride and Proton Transfer Outside the Coordination Sphere of the Metal

  摘要：

  Reduction of imines by [2,5-Ph-2-3,4-Tol(2)(eta(5)-C4COH)]Ru(CO)H-2 (2) produces kinetically stable ruthenium amine complexes. Reduction of an imine by 2 in the presence of an external amine trap gives only the complex of the newly generated amine. Reaction of 2 with H2N-p-C6H4N=CHPh (11), which contains an intramolecular amine trap, gave a 1:1 mixture of [2,5-Ph-2-3,4-Tol(2)(eta(4)-C4CO)](CO)(2)RuNH(CH2Ph)(C6H4-p-NH2) (8), formed by coordination of the newly generated amine to the ruthenium center, and [2,5-Ph-2-3,4-Tol(2)(eta(4)-C4CO)](CO)(2)RuNH2C6H4-p-NHCH2Ph (9), formed by coordination of the amine already present in the substrate. These results require transfer of hydrogen to the imine outside the coordination sphere of the metal to give a coordinatively unsaturated intermediate that can be trapped inside the initial solvent cage. Amine diffusion from the solvent cage must be much slower than coordination to the metal center. Mechanisms requiring prior coordination of the substrate to ruthenium would have led only to 8 and can be eliminated.

  DOI：

  10.1021/ja053956o
• 作为试剂：
  描述：

  对甲基苯甲醛 、 频那醇硼烷 在 [[2,5-Ph2-3,4-Tol2-(η4-C4CO)]Ru(CO)2]2 作用下， 以 氘代苯 为溶剂， 生成 4,4,5,5-tetramethyl-2-((4-methylbenzyl)oxy)-1,3,2-dioxaborolane
  参考文献：
  名称：

  Shvo加氢催化剂的硼取代类似物：醛，亚胺和酮的催化加氢硼化

  摘要：

  硼-取代的钌hydroxycycylopentadienyl氢化[2,5-PH 2 -3,4-托尔2（η 5 -C 4 COBpin）的Ru（CO）2 H]（BPIN = 4,4,5,5-四甲基-1- -1,3,2-二氧硼戊环）5通过加入频哪醇的钌二聚体[2,5-PH合成2 -3,4-托尔2（η 5 -C 4 CO）的Ru（CO）2 ] 2 4。复杂5在化学计量和催化上与醛反应，在温和的反应条件下提供硼氢化产物。对位取代的苯甲醛的Hammett相关图提供了+0.91的ρ值。芳基亚胺的催化加氢硼化提供相应胺的高产率。然而，芳基酮的氢硼化需要强烈的吸电子取代基以在合理的反应时间内诱导氢硼化。

  DOI：

  10.1021/om801228m

文献信息

• Isomerization and Deuterium Scrambling Evidence for a Change in the Rate-Limiting Step during Imine Hydrogenation by Shvo's Hydroxycyclopentadienyl Ruthenium Hydride
  作者：Charles P. Casey、Jeffrey B. Johnson

  DOI：10.1021/ja044450t

  日期：2005.2.1

  mechanism analogous to that proposed for aldehyde and ketone reduction. Reduction of electron-rich N-alkyl-substituted imine, N-isopropyl-(4-methyl)benzilidene amine (9), was accompanied by facile imine isomerization and scrambling of deuterium labels from reduction with 5-RuDOH into the N-alkyl substituent of both the amine complex and into the recovered imine. Inverse equilibrium isotope effects were

  羟基环戊二烯基氢化钌 5 可在室温以下有效还原亚胺。氮上更好的供体取代基导致更快的速率和速率决定步骤从氢转移到胺配位的转变。在 11 摄氏度时减少缺电子 N-亚苄基五氟苯胺 (8) 导致游离胺和 k(OH)/k(OD) = 1.61 +/- 0.08 的动力学同位素效应，k(RuH)/k(RuD) = 2.05 +/- 0.08 和 k(RuHOH)/k(RuDOD) = 3.32 +/- 0.14，表明限速协同氢转移，类似于醛和酮还原提出的机制。还原富电子的 N-烷基取代亚胺、N-异丙基-(4-甲基)联苯胺(9)、伴随着容易的亚胺异构化和氘标记从 5-RuDOH 还原到胺复合物的 N-烷基取代基和回收的亚胺中的混乱。在 -48 摄氏度的 N-亚苄基-叔丁胺 (11) 还原中观察到逆平衡同位素效应 (k(OH)/k(OD) = 0.89 +/- 0.06, k(RuH)/k(RuD) ) =
• A Three-Stage Mechanistic Model for Ammonia–Borane Dehydrogenation by Shvo’s Catalyst
  作者：Zhiyao Lu、Brian L. Conley、Travis J. Williams

  DOI：10.1021/om300562d

  日期：2012.10.8

  We propose a mechanistic model for three-stage dehydrogenation of ammonia borane (AB) catalyzed by Shvo's cyclopentadienone-ligated ruthenium complex. We provide evidence for a plausible mechanism for catalyst deactivation, the transition from fast catalysis to slow catalysis, and relate those findings to the invention of a second-generation catalyst that does not suffer from the same deactivation

  我们提出了一种由Shvo的环戊二烯酮连接的钌络合物催化的三级氨硼烷（AB）脱氢的机理模型。我们提供了催化剂失活的合理机制，从快速催化到缓慢催化的过渡的证据，并将这些发现与第二代催化剂的发明相提并论。第二代催化剂没有遭受相同的失活化学反应。催化剂失活的主要机理是硼嗪介导的钌物种的氢硼化是快速催化情况下的活性氧化剂。该转变的特征在于反应速率规律的变化和催化剂的表观静止状态的变化。同样，在这种缓慢的催化情况下，我们看到了硼，氮物种，氨基二硼烷序列中的另一种中间体。