[2,5-Ph2-3,4-Tol2(η4-C4CO)]Ru(CO)2NHMe(CH2Ph) | 333382-71-1

• 英文名称: [2,5-Ph2-3,4-Tol2(η4-C4CO)]Ru(CO)2NHMe(CH2Ph)
• 英文别名: [2,5-diphenyl-3,4-(di-p-tolyl)(η4-C4CO)]Ru(CO)2NH(Me)(CH2Ph)；[2,5-Ph2-3,4-Tol2(η4-C4CO)](CO)2Ru(N-methylbenzylamine)；[2,5-Ph2-3,4-Tol2-(η4-C4CO)]Ru(CO)2[NH(CH2Ph)(CH3)]
• CAS: 333382-71-1
• 化学式: C₄₁H₃₅NO₃Ru
• 分子量: 690.804
• InChiKey: PREKLCVDAVEIQQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 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：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  [[2,5-Ph2-3,4-Tol2-(η4-C4CO)]Ru(CO)2]2 、 N-甲基苄胺 以 二氯甲烷-D2 为溶剂， 以79%的产率得到[2,5-Ph2-3,4-Tol2(η4-C4CO)]Ru(CO)2NHMe(CH2Ph)
  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

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) ) =
• Hydrogen Transfer to Carbonyls and Imines from a Hydroxycyclopentadienyl Ruthenium Hydride:  Evidence for Concerted Hydride and Proton Transfer
  作者：Charles P. Casey、Steven W. Singer、Douglas R. Powell、Randy K. Hayashi、Michael Kavana

  DOI：10.1021/ja002177z

  日期：2001.2.1

  Reaction of ([2,5-Ph(2)-3,4-Tol(2)(eta(5)-C(4)CO)](2)H)Ru(2)(CO)(4)(mu-H) (6) with H(2) formed [2,5-Ph(2)-3,4-Tol(2)(eta(5)-C(4)COH)Ru(CO)(2)H] (8), the active species in catalytic carbonyl reductions developed by Shvo. Kinetic studies of the reduction of PhCHO by 8 in THF at -10 degrees C showed second-order kinetics with Delta H(double dagger) = 12.0 kcal mol(-1) and Delta S(double dagger) = -28

  ([2,5-Ph(2)-3,4-Tol(2)(eta(5)-C(4)CO)](2)H)Ru(2)(CO)(4)( mu-H) (6) 与 H(2) 形成 [2,5-Ph(2)-3,4-Tol(2)(eta(5)-C(4)COH)Ru(CO)(2) H] (8)，Shvo 开发的催化羰基还原中的活性物质。PhCHO 在-10 摄氏度的 THF 中减少 8 的动力学研究表明二阶动力学与 Delta H（双匕首）= 12.0 kcal mol(-1) 和三角洲 S（双匕首）= -28 eu。CF(3)CO(2)H 不会加速还原速率，并且不会被 CO 抑制。8 中 RuH 和 OH 位置的选择性氘化产生了单独的动力学同位素效应 k(RuH)/k(RuD) = 1.5 +/- 0.2 和 k(OH)/k(OD) = 2.2 +/- 0.1 用于 PhCHO 在 0 摄氏度的还原。同时氘化 8 中的两个位置给出了
• Stereochemistry of Imine Reduction by a Hydroxycyclopentadienyl Ruthenium Hydride
  作者：Charles P. Casey、Galina A. Bikzhanova、Ilia A. Guzei

  DOI：10.1021/ja056402u

  日期：2006.2.1

  The stereochemistry of hydrogen transfer from [2,5-Ph(2)-3,4-Tol(2)(eta(5)-C(4)COD)]Ru(CO)(2)D to N-aryl imines to give amine complexes was shown to be mostly trans stereospecific. Stereospecific hydrogen transfer is proposed to generate an amine and a coordinatively unsaturated ruthenium intermediate in close proximity. Coordination of the amine is proposed to occur faster than lone pair inversion

  [2,5-Ph(2)-3,4-Tol(2)(eta(5)-C(4)COD)]Ru(CO)(2)D 到 N-芳基亚胺的氢转移立体化学产生胺复合物被证明主要是反式立体定向的。提出立体有择氢转移以产生胺和紧邻的配位不饱和钌中间体。提出胺的配位比胺的孤对反转发生得更快。相比之下，氢转移到 N-烷基亚胺是立体无规的。提出立体化学丢失的部分原因是氢转移的可逆性比胺配位快。