[Cp*Rh(CH3)2(pyridine)] | 801311-36-4

• 英文名称: [Cp*Rh(CH3)2(pyridine)]
• 英文别名: [RhCp(*)(pyridine)Me2]
• CAS: 801311-36-4
• 化学式: C₁₇H₂₆NRh
• 分子量: 347.306
• InChiKey: GQMQQQHEFDCXIK-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

• 作为反应物：
  描述：

  (pentamethylcyclopentadienyl)gallium(I) 、 [Cp*Rh(CH3)2(pyridine)] 以 not given 为溶剂， 生成 [RhCp(*)(C5Me4GaMe3)]
  参考文献：
  名称：

  低价第 13 族有机基的过渡金属化学

  摘要：

  低价13族有机基的配位EIR [E = Al, Ga, In; R = Cp*, C(SiMe3)3] 过渡金属在过去十年中引起了越来越多的兴趣。这些新配体与许多过渡金属的配合物和簇合物已被分离和表征。EIR 部分在形式上与 CO 和 PR3（R = 烷基，Cp*）或卡宾（R = 螯合基团）具有不同的 σ-供体和 π-受体性质，具体取决于有机基团 R 和第 13 族金属 E在这篇综述中，描述了形成 M-E 键的不同方式，例如不稳定配体的取代反应或 EIR 插入过渡金属卤化物键。此外，还讨论了均质配合物 Ma(EIR)b 的反应性，概述了这些新配合物类型在键活化反应中的用途。(© Wiley-VCH Verlag GmbH &

  DOI：

  10.1002/ejic.200400569
• 作为产物：
  描述：

  吡啶 、 dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer 、 Dimethylzinc 以 四氢呋喃 、 甲苯 为溶剂， 以77%的产率得到[Cp*Rh(CH3)2(pyridine)]
  参考文献：
  名称：

  Mechanistic Insights into an Unprecedented C−C Bond Activation on a Rh/Ga Bimetallic Complex:  A Combined Experimental/Computational Approach

  摘要：

  The unusual rearrangement of [RhCp*(GaCp*)(CH3)(2)] (1c) to [RhCp*(C5Me4Ga(CH3)(3))] (2) is presented and its mechanism is discussed in detail. C-13 MAS NMR spectroscopy revealed that the title reaction proceeds cleanly not only in solution but also in solid state, which supports a unimolecular reaction pathway. On the basis of H-1, C-13, and ROESY NMR spectroscopy as well as isolation and structural elucidation of the hydrolysis product, the compound [RhCp*(endo-eta(4)-C5Me5GaMe2)] (3a) was identified as a crucial reaction intermediate. DFT calculations on the B3LYP level of theory support this assignment and suggest a concerted C-C bond activation mechanism that topologically takes place at the gallium center. Furthermore, two fluxional processes of the reaction intermediate 3a were studied experimentally as well as by computational methods. First, a mechanism takes place similar to a ring-slipping process that exchanges a GaMe2 group between adjacent ring carbon atoms within the same Cp* ring. This process proceeds at a rate comparable to the NMR time scale and indeed is calculated to be energetically very favorable. Second, a unimolecular exchange process of the GaMe2 group between the two Cp* rings of 3a could be experimentally proven by the introduction of phenyl substituents as a label into the Cp* ligands at both sites, the rhodium as well as the gallium center. A series of experiments including deuteration studies and competition reactions was performed to substantiate the suggested mechanism being in accordance with DFT calculations on possible transition states.

  DOI：

  10.1021/ja055298d

文献信息

• The reaction of RhCp*(CH₃)₂(L) (L = pyridine, dmso) with GaCp* and AlCp*: A new type of carbon–carbon bond activation reaction
  作者：Thomas Cadenbach、Christian Gemel、Rochus Schmid、Stefan Block、Roland A. Fischer

  DOI：10.1039/b410077h

  日期：——

  Reaction of RhCp*(L)(CH3)2 (L = pyridine, dmso) with equimolar amounts of GaCp* at 60 °C quantitatively leads to the zwitterionic species [Cp*Rh(CpMe4GaMe3)]. [Cp*Rh(CH3)2(GaCp*)] could be isolated and identified as an intermediate in this reaction.

  RhCp*(L)(CH3)2 的反应 (L = 吡啶, dmso) 与等摩尔量的 GaCp* 在 60 °C 下定量产生两性离子物质 [Cp*Rh(CpMe4GaMe3)]。 [Cp*Rh( )2(GaCp*)] 可以被分离并鉴定为该反应中的中间体。