[RhCp(*)(endo-η4-C5Me5GaMe2)] | 801311-34-2

• 英文名称: [RhCp(*)(endo-η4-C5Me5GaMe2)]
• CAS: 801311-34-2
• 化学式: C₂₂H₃₆GaRh
• 分子量: 473.156
• InChiKey: KKXMXBNGYTYMGF-UHFFFAOYSA-N

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：

  [RhCp(*)(endo-η4-C5Me5GaMe2)] 以 吡啶 为溶剂， 生成 [RhCp(*)(C5Me4GaMe3)]
  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
• 作为产物：
  描述：

  [RhCp(*)(GaCp(*))Me2] 以 氘代吡啶 为溶剂， 生成 [RhCp(*)(endo-η4-C5Me5GaMe2)]
  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