| 1598374-33-4

• CAS: 1598374-33-4
• 化学式: C₂₀H₃₆ClNPRh
• 分子量: 459.845
• InChiKey: MCDQSJXQUCFXAQ-ONEVTFJLSA-M

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：

  、 silver tetrafluoroborate 以 四氢呋喃 为溶剂， 反应 1.0h， 以80%的产率得到
  参考文献：
  名称：

  Chemistry of transition-metal complexes containing functionalized phosphines. Part 2. Cationic rhodium(I) complexes stabilized by hemilabile diallylphosphines

  摘要：

  Cationic rhodium(I) complexes of the type [Rh(COD){k(3)(P,C,C)-RP(CH2CH=CH2)(2)}][BF4] (R = Bu-t 3a, Ph 3b, (i)Pr2N 3c) have been synthesized starting from the chloro-bridged dimer [Rh-2(mu-Cl)(2)(COD)(2)] and fully characterized by P-31{H-1}, H-1 and C-13{H-1} NMR. X-ray diffraction analysis of 3a and 3c showed a square planar geometry around of the rhodium atom, with allyl-phosphine ligands in a chelating fashion due to coordination of only one of the allylic double bonds while the other allyl moiety is located away from the metal center. Crystals of 3c showed the presence of the two enantiomers in the asymmetric unit. In solution, a dynamic equilibrium of exchange between the two allylic double bonds was detected by low temperature NMR analysis. Hemilabile properties of diallylphosphine ligands have been demonstrated by ligand exchange reactions and the reversible displacement of coordinated allylic double bond by acetonitrile have been observed. DFT calculations have been performed to explain the order of reactivity on removing the acetonitrile ligand under high vacuum. (C) 2014 Published by Elsevier B.V.

  DOI：

  10.1016/j.ica.2014.02.011
• 作为产物：
  描述：

  diallyl(diisopropylamino)phosphine 、 chloro(1,5-cyclooctadiene)rhodium(I) dimer 以 二氯甲烷 为溶剂， 反应 1.0h， 以98%的产率得到
  参考文献：
  名称：

  Chemistry of transition-metal complexes containing functionalized phosphines. Part 2. Cationic rhodium(I) complexes stabilized by hemilabile diallylphosphines

  摘要：

  Cationic rhodium(I) complexes of the type [Rh(COD){k(3)(P,C,C)-RP(CH2CH=CH2)(2)}][BF4] (R = Bu-t 3a, Ph 3b, (i)Pr2N 3c) have been synthesized starting from the chloro-bridged dimer [Rh-2(mu-Cl)(2)(COD)(2)] and fully characterized by P-31{H-1}, H-1 and C-13{H-1} NMR. X-ray diffraction analysis of 3a and 3c showed a square planar geometry around of the rhodium atom, with allyl-phosphine ligands in a chelating fashion due to coordination of only one of the allylic double bonds while the other allyl moiety is located away from the metal center. Crystals of 3c showed the presence of the two enantiomers in the asymmetric unit. In solution, a dynamic equilibrium of exchange between the two allylic double bonds was detected by low temperature NMR analysis. Hemilabile properties of diallylphosphine ligands have been demonstrated by ligand exchange reactions and the reversible displacement of coordinated allylic double bond by acetonitrile have been observed. DFT calculations have been performed to explain the order of reactivity on removing the acetonitrile ligand under high vacuum. (C) 2014 Published by Elsevier B.V.

  DOI：

  10.1016/j.ica.2014.02.011