| 945485-82-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• CAS: 945485-82-5
• 化学式: C₃₄H₃₃N₂O₆PRh₂
• 分子量: 802.431
• InChiKey: PSARPCRCNDWDAS-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 、 Rh2(acetato)3[(C6H4)P(C6H5)2](H2O)2 以 not given 为溶剂， 生成
  参考文献：
  名称：

  Determination of Equilibrium Constants and Computational Interaction Energies for Adducts of [Rh₂(RCO₂)_4-n(PC)_n] (n = 0−2) with Lewis Bases

  摘要：

  Properties of dirhodium catalysts with cyclometalated aryl phosphine ligands have been studied. We report here the study of the acid-base reaction of Rh-2(RCO2)(2)(PC)(2)(H2O)(2) catalysts (PC = cyclometalated aryl phosphine) with different Lewis bases. The determination of the equilibrium constants of these reactions can be used to study to which extent the properties of the axial coordination site of the catalyst, considered the active site, are affected by modification of the metalated phosphines, the carboxylate ligands, or the incoming axial ligand. The trends in the computational density functional theory interaction energies show good agreement with the major trends in the equilibrium constants, thus enabling a further study of the influence of the modification of the ligand core.

  DOI：

  10.1021/ic062171w

文献信息

• A unified mechanistic view obtained from the temperature and pressure dependence of the spontaneous, acid-, and base-assisted cyclometallation reactions of dirhodium(<scp>II</scp>) complexes
  作者：Francisco Estevan、Gabriel González、Pascual Lahuerta、Manuel Martinez、Eduardo Peris、Rudi van Eldik

  DOI：10.1039/dt9960001045

  日期：——

  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.