| 945485-81-4

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• CAS: 945485-81-4
• 化学式: C₃₇H₃₉N₂O₆PRh₂
• 分子量: 844.511
• InChiKey: GUPSRQUGVSUOFW-UHFFFAOYSA-K

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：

  吡啶 、 以 甲苯 为溶剂， 生成 、
  参考文献：
  名称：

  A unified mechanistic view obtained from the temperature and pressure dependence of the spontaneous, acid-, and base-assisted cyclometallation reactions of dirhodium(II) complexes

  摘要：

  The reaction of compounds [Rh-2(O(2)CMe)(mu-O(2)CMe)(2) {mu-(XC(6)H(3))P(C(6)H(4)X-p)(2)}{P(C(6)H(4)X'-p)(3)}] (X = H, X' = H or Me; X = Me, X' = H or Me), having a metallated and an equatorial phosphine in a head-to-tail cisoid configuration, to produce the corresponding doubly metallated compounds [Rh-2(mu-O(2)CMe)(2)-{mu-(XC(6)H(3))P(C(6)H(4)X-p)(2)}(2)], has been studied in detail. The thermal, acid-, and base-assisted conditions include toluene solution, neat acetic acid, and different bases [PPh(3), P(C(6)H(4)Me-p)(3) or pyridine] in toluene solution and as a function of temperature, pressure and base concentration when applicable). The doubly metallated compounds always show retention of the head-to-tail cisoid configuration according to P-31 NMR spectroscopy. The reported activation parameters allow a clear differentiation between the spontaneous, acid-assisted and base-assisted processes, some of which had been previously studied (Delta H-double dagger = 80 +/- 5, 68 +/- 1, 38 +/- 3 kJ mol(-1); Delta S-double dagger = -105 +/- 15, -85 +/- 3, 150 +/- 30 J K-1 mol(-1); Delta V-double dagger = -22.7 +/- 0.2, -15.3 +/- 0.2, -35.0 +/- 0.5 cm(3) mol(-1) respectively, for the compound with X X' = H). For the reactions under base-assisted conditions, when long reaction times and/or high added Lewis-base concentrations were applied, the non-metallated phosphine was displaced from equatorial to axial co-ordination. Under these conditions a : mixture of the bis adducts of the monometallated [Rh-2(mu-O(2)CMe)(3){mu-(XC(6)H(3))P(C(6)H(4)X-p)(2)}], and the doubly-metallated compounds was detected by P-31 NMR spectroscopy. The activation parameters obtained for this slower process agree with those expected for substitution reactions and are interpreted in terms of the steric demands of the mono and bis adducts formed immediately on mixing the reaction solutions.

  DOI：

  10.1039/dt9960001045