[(tMe-Rucaphosphite)Rh(H)(CO)₂] | 1421870-15-6

• 英文名称: [(tMe-Rucaphosphite)Rh(H)(CO)₂]
• CAS: 1421870-15-6
• 化学式: C₅₀H₄₅O₈P₂Rh
• 分子量: 938.756
• InChiKey: AOJOHMHZMBTZGS-NBJICOIQSA-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

• 作为产物：
  描述：

  acetylacetonatodicarbonylrhodium(l) 、 2,4,8,10-Tetramethyl-6-[[13-(2,4,8,10-tetramethylbenzo[d][1,3,2]benzodioxaphosphepin-6-yl)oxy-3-tetracyclo[6.6.2.02,7.09,14]hexadeca-2(7),3,5,9(14),10,12-hexaenyl]oxy]benzo[d][1,3,2]benzodioxaphosphepine 、 氢气 在 一氧化碳 作用下， 以 氘代甲苯 为溶剂， 90.0 ℃ 、1.2 MPa 条件下， 反应 2.0h， 生成 [(tMe-Rucaphosphite)Rh(H)(CO)₂] 、 [(tMe-Rucaphosphite)Rh(H)(CO)₂]
  参考文献：
  名称：

  Inter- and Intramolecular Interactions in Triptycene-Derived Bisphosphite Hydroformylation Catalysts: Structures, Energies, and Caveats for DFT-Assisted Ligand Design

  摘要：

  The hydroformylation catalyst (L)RhH(CO)(2), with a triptycene-derived bisphosphite ligand, and its iridium analogue were studied in solution, in the solid state, and computationally (DFT) in order to determine their molecular structures and to understand the equilibria between isomers. The predicted intramolecular distance of the two biphenyl side groups of these ligands strongly depends upon the treatment of inter- and intramolecular noncovalent interactions. A balanced treatment of these "weak" interactions is a prerequisite for obtaining reasonable structures and consequently also for determining relative energies of the different P-coordination modes. Low-temperature NMR studies confirm the equilibrium between axial-equatorial and equatorial-equatorial isomers in solution and have been used to estimate their relative stability in the equilibrium.

  DOI：

  10.1021/om301027x

文献信息

• Iridium Models of Rhodium Intermediates in Hydroformylation Catalysis: Isolation and Molecular Structures of Fluxional ae and ee Isomers
  作者：Golnar Abkai、Sebastian Schmidt、Tobias Rosendahl、Frank Rominger、Peter Hofmann

  DOI：10.1021/om401139u

  日期：2014.6.23

  (equatorial–equatorial) ligand P coordination and fluxional behavior in solution. L2 is a new chelating bisphosphite with unprecedented high selectivity in Rh-catalyzed bis-hydroformylation of butadiene to adipic aldehyde. These Ir analogues are ideal stabilized structural models for nonseparable ae and ee Rh-hydroformylation resting state isomers [(L2)Rh(H)(CO)2]. With Ir, both stereoisomers with

  我们报道了具有ae（轴向-赤道）和ee（赤道-赤道）配体的三角-双锥体氢化二羰基二羰Ir配合物[（L 2）Ir（H）（CO）2 ]的两种立体异构体的合成和单晶分子结构溶液中的P配位和通量行为。L 2是一种新型的螯合双亚磷酸酯，在Rh催化的丁二烯双加氢甲酰化为己二醛中具有空前的高选择性。这些Ir类似物是不可分离的ae和ee Rh加氢甲酰基化静止状态异构体[（L 2）Rh（H）（CO）2 ]的理想稳定结构模型。使用Ir可以首次对具有相同配体的两种立体异构体进行独立表征。
• Rhodium-Catalyzed Hydroformylation of 1,3-Butadiene to Adipic Aldehyde: Revealing Selectivity and Rate-Determining Steps
  作者：Sebastian Schmidt、Eszter Baráth、Christoph Larcher、Tobias Rosendahl、Peter Hofmann

  DOI：10.1021/om501015z

  日期：2015.3.9