[Rh(α,α'-bis(diethylphosphino)xylene)2](CF3SO3) | 834918-16-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: [Rh(α,α'-bis(diethylphosphino)xylene)2](CF3SO3)
• CAS: 834918-16-0
• 化学式: CF₃O₃S*C₃₂H₅₆P₄Rh
• 分子量: 816.668
• InChiKey: NQUVMSFZODWWQM-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  11.51
• 重原子数：
  45.0
• 可旋转键数：
  8.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  57.2
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  [Rh(α,α'-bis(diethylphosphino)xylene)2](CF3SO3) 、 氢气 在 t-BuOK 作用下， 以 乙腈 为溶剂， 以70%的产率得到[HRh(α,α'-bis(diethylphosphino)xylene)2]
  参考文献：
  名称：

  Thermodynamic Studies of HRh(depx)₂ and [(H)₂Rh(depx)₂](CF₃SO₃):  Relationships between Five-Coordinate Monohydrides and Six-Coordinate Dihydrides

  摘要：

  Four new rhodium complexes, [Rh(depx)(2)](CF3SO3), [(H)(2)Rh(depx)(2)](CF3SO3),[HRh(dePX)(2)(CH3CN)](CF3SO3)(2), and HRh(depx)(2) (where depx = alpha,alpha'-bis(diethylphosphino)xylene), have been synthesized and characterized. The pK(a) values of [(H)(2)Rh(depx)(2)](+) (30.6 +/- 0.3) and [HRh(depx)(2)(CH3CN)](2+) (11.5 +/- 0.4) in acetonitrile were determined by equilibrium reactions with appropriate bases. The hydride donor ability of [(H)(2)Rh(depx)(2)](+) (71.6 +/- 1.0 kcal/mol) was determined by the heterolytic cleavage of hydrogen by [HRh(depx)(2)(CH3CN)](2+) to form [(H)(2)Rh(depx)(2)](+) in the presence of thioacetamide or benzamide. These equilibrium measurements, the half-wave potentials for the Rh(+1/0) and Rh(0/-1) couples of [Rh(depx)(2)](+), and the reversible one-electron oxidation of HRh(depx)(2) (all measured at 22 +/- 1.5 degreesC) were used to establish nine heterolytic and homolytic bond-dissociation free energies in acetonitrile. From these relationships, and those established previously for analogous cobalt and platinum complexes, we conclude that the homolytic bond-dissociation free energies of six-coordinate dihydride species are approximately 2 kcal/mol less than those of the corresponding five-coordinate monohydride species derived by deprotonation. Similarly, the pK(a) values of six-coordinate dihydride complexes are approximately 2 units lower than the corresponding five-coordinate species formally derived by homolytic bond cleavage.

  DOI：

  10.1021/om049437w
• 作为产物：
  描述：

  [HRh(α,α'-bis(diethylphosphino)xylene)2(CH3CN)](CF3SO3)2 在 p-CH₃OC₆H₄NH₂ 作用下， 以 氘代乙腈 为溶剂， 生成 [Rh(α,α'-bis(diethylphosphino)xylene)2](CF3SO3)
  参考文献：
  名称：

  Thermodynamic Studies of HRh(depx)₂ and [(H)₂Rh(depx)₂](CF₃SO₃):  Relationships between Five-Coordinate Monohydrides and Six-Coordinate Dihydrides

  摘要：

  Four new rhodium complexes, [Rh(depx)(2)](CF3SO3), [(H)(2)Rh(depx)(2)](CF3SO3),[HRh(dePX)(2)(CH3CN)](CF3SO3)(2), and HRh(depx)(2) (where depx = alpha,alpha'-bis(diethylphosphino)xylene), have been synthesized and characterized. The pK(a) values of [(H)(2)Rh(depx)(2)](+) (30.6 +/- 0.3) and [HRh(depx)(2)(CH3CN)](2+) (11.5 +/- 0.4) in acetonitrile were determined by equilibrium reactions with appropriate bases. The hydride donor ability of [(H)(2)Rh(depx)(2)](+) (71.6 +/- 1.0 kcal/mol) was determined by the heterolytic cleavage of hydrogen by [HRh(depx)(2)(CH3CN)](2+) to form [(H)(2)Rh(depx)(2)](+) in the presence of thioacetamide or benzamide. These equilibrium measurements, the half-wave potentials for the Rh(+1/0) and Rh(0/-1) couples of [Rh(depx)(2)](+), and the reversible one-electron oxidation of HRh(depx)(2) (all measured at 22 +/- 1.5 degreesC) were used to establish nine heterolytic and homolytic bond-dissociation free energies in acetonitrile. From these relationships, and those established previously for analogous cobalt and platinum complexes, we conclude that the homolytic bond-dissociation free energies of six-coordinate dihydride species are approximately 2 kcal/mol less than those of the corresponding five-coordinate monohydride species derived by deprotonation. Similarly, the pK(a) values of six-coordinate dihydride complexes are approximately 2 units lower than the corresponding five-coordinate species formally derived by homolytic bond cleavage.

  DOI：

  10.1021/om049437w