| 199342-69-3

• CAS: 199342-69-3
• 化学式: C₃₆H₁₇F₂₄IrO₂P₂
• 分子量: 1191.66
• InChiKey: UDFJWIVEOSVICI-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

• 作为产物：
  描述：

  fac-[DIPHOS-(3,5-CF3)]Ir(CO)H3 以 苯 为溶剂， 以67%的产率得到
  参考文献：
  名称：

  Electron Withdrawing Substituents on Equatorial and Apical Phosphines Have Opposite Effects on the Regioselectivity of Rhodium Catalyzed Hydroformylation

  摘要：

  The electronic effects of electron withdrawing aryl substituents on equatorial and apical diphosphines were investigated. Chelating diphosphines designed to coordinate in diequatorial or in apical-equatorial positions were synthesized, and their effects on the regioselectivity of rhodium catalyzed 1-hexene hydroformylation were observed. Only diequatorial coordination was observed for 2,2'-bis[(diphenylphosphino)methyl]-1,1'-biphenyl (BISBI) complexes (BISBI)Ir(CO)(2)H (8) and [BISBI-(3,5-CF3)]Ir(CO)(2)H (10), and only apical-equatorial coordination was seen for 1,2-bis(diphenylphosphino)ethane (DIPHOS) complexes (DIPHOS)Ir(CO)(2)H (14) and [DIPHOS-(3,5-CF3)]Ir(CO)(2)H (15). For the trans-1,2-bis [(diphenylphosphino)methyl] cyclopropane (T-BDCP) complexes, a mixture of diequatorial and apical-equatorial complexes was seen. For (T-BDCP)Ir(CO)(2)H (12), 12-ee was favored over 12-ee by 63:37, but for [T-BDCP-(3,5-CF3)]Ir(CO)(2)H (13) the conformational preference was reversed and a 10:90 ratio of 13-ee:13-ee was seen. The electron withdrawing groups in the equatorial positions of BISBI-(3,5-CF3) (1) and T-BDCP-(3,5-CF3) (2) led to an increase in n-aldehyde regioselectivity in rhodium catalyzed hydroformylation. However, electron withdrawing aryl substituents in the apical positions of DIPHOS-(3,5-CF3) (3) led to a decrease in n-aldehyde regioselectivity in rhodium catalyzed hydroformylation.

  DOI：

  10.1021/ja9719440