trans-[RhCl(P(OPh)3)(PPh3)2] | 1400872-38-9

• 英文名称: trans-[RhCl(P(OPh)3)(PPh3)2]
• CAS: 1400872-38-9
• 化学式: C₅₄H₄₅ClO₃P₃Rh
• 分子量: 973.229
• InChiKey: GLUWAKDXUKJTEC-UHFFFAOYSA-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：

  一氧化碳 、 trans-[RhCl(P(OPh)3)(PPh3)2] 以 二氯甲烷 、 丙酮 为溶剂， 生成 反式-双(三苯基膦)合氯化羰基铑(Ⅰ)
  参考文献：
  名称：

  Modification of Wilkinson’s catalyst with triphenyl phosphite: Synthesis, structure, 31P NMR and DFT study of trans-[RhCl(P(OPh)3)(PPh3)2]

  摘要：

  The complex trans-[RhCl(P(OPh)(3))(PPh3)(2)] (1) has been prepared and characterized by P-31 NMR spectroscopy and single crystal X-ray crystallography. It was found that in the solid state there are two forms of complex 1 in the unit cell forming a cocrystal. DFT theoretical computations have confirmed the existence of the two forms and have provided evidence for the greater stability of 1 compared with Wilkinson's catalyst, [RhCl(PPh3)(3)] (2), in terms of the dissociation energy of the Rh-P(PPh3) bonds. On the basis of the phosphorus chemical shifts, delta(P-pPh3), and the results of the theoretical computations, it is suggested that the Rh-P(PPh3) bonding interactions are slightly enhanced in 1 compared with 2. A distinct difference between complexes 1 and 2, was found to be the catalytic activity of 1 in the alkylation of allyl acetate with sodium diethylmalonate, while 2 is almost catalytically inefficient. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2012.06.086
• 作为产物：
  描述：

  亚磷酸三苯酯 、 Wilkinson's catalyst 以 乙腈 为溶剂， 反应 24.0h， 以95%的产率得到trans-[RhCl(P(OPh)3)(PPh3)2]
  参考文献：
  名称：

  Modification of Wilkinson’s catalyst with triphenyl phosphite: Synthesis, structure, 31P NMR and DFT study of trans-[RhCl(P(OPh)3)(PPh3)2]

  摘要：

  The complex trans-[RhCl(P(OPh)(3))(PPh3)(2)] (1) has been prepared and characterized by P-31 NMR spectroscopy and single crystal X-ray crystallography. It was found that in the solid state there are two forms of complex 1 in the unit cell forming a cocrystal. DFT theoretical computations have confirmed the existence of the two forms and have provided evidence for the greater stability of 1 compared with Wilkinson's catalyst, [RhCl(PPh3)(3)] (2), in terms of the dissociation energy of the Rh-P(PPh3) bonds. On the basis of the phosphorus chemical shifts, delta(P-pPh3), and the results of the theoretical computations, it is suggested that the Rh-P(PPh3) bonding interactions are slightly enhanced in 1 compared with 2. A distinct difference between complexes 1 and 2, was found to be the catalytic activity of 1 in the alkylation of allyl acetate with sodium diethylmalonate, while 2 is almost catalytically inefficient. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2012.06.086
• 作为试剂：
  描述：

  乙酸烯丙酯 、 丙二酸二乙酯 在 sodium hydride 、 trans-[RhCl(P(OPh)3)(PPh3)2] 作用下， 以 四氢呋喃 为溶剂， 反应 19.0h， 生成 烯丙基丙二酸二乙酯
  参考文献：
  名称：

  Modification of Wilkinson’s catalyst with triphenyl phosphite: Synthesis, structure, 31P NMR and DFT study of trans-[RhCl(P(OPh)3)(PPh3)2]

  摘要：

  The complex trans-[RhCl(P(OPh)(3))(PPh3)(2)] (1) has been prepared and characterized by P-31 NMR spectroscopy and single crystal X-ray crystallography. It was found that in the solid state there are two forms of complex 1 in the unit cell forming a cocrystal. DFT theoretical computations have confirmed the existence of the two forms and have provided evidence for the greater stability of 1 compared with Wilkinson's catalyst, [RhCl(PPh3)(3)] (2), in terms of the dissociation energy of the Rh-P(PPh3) bonds. On the basis of the phosphorus chemical shifts, delta(P-pPh3), and the results of the theoretical computations, it is suggested that the Rh-P(PPh3) bonding interactions are slightly enhanced in 1 compared with 2. A distinct difference between complexes 1 and 2, was found to be the catalytic activity of 1 in the alkylation of allyl acetate with sodium diethylmalonate, while 2 is almost catalytically inefficient. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2012.06.086