| 328924-77-2

• CAS: 328924-77-2；328924-79-4；328530-76-3
• 化学式: BF₄*C₂₂H₅₄P₄Rh
• 分子量: 632.276
• InChiKey: NIQLZGNSIDITHB-HHSMFLHPSA-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：

  [(R,R)-(MetBuPCH2PMetBu)2Rh]BF4 、 氢气 以 氘代甲醇 为溶剂， 生成
  参考文献：
  名称：

  Reaction of a Rhodium−MiniPHOS Complex with Dihydrogen:  NMR and Computational Study

  摘要：

  The rhodium-MiniPHOS complex [Rh((R,R)-(MeBuPCH2PMeBut)-P-t)(2)](+) BF4- (1) is reversibly and stereoselectively hydrogenated at low temperatures to give one isomer of cis-dihydride 2a. The second possible diastereomer, 2b, is not observed experimentally. DFT calculations suggest that 2b is 3.5 kcal mol(-1) less stable than 2a. The parameters of the equilibrium between 2a, 1, and H-2 determined by NMR are DeltaH = -7.7 +/- 0.1 kcal mol(-1) and DeltaS = -25 +/- 1 cal mol(-1) K-1. Formation of the trans-dihydride 3 is observed at around -20 degreesC. Most probably 3 is formed by isomerization of 2a or 2b. This isomerization involves reversible dissociation of the Rh-P bond. Similar dissociation of the Rh-P bond in 2a might make possible the substrate binding when 1 is used as a catalyst for asymmetric hydrogenation.

  DOI：

  10.1021/om000304u