[1-[2-(2-Diphenylphosphanylimidazol-1-yl)phenyl]imidazol-2-yl]-diphenylphosphane | 1159579-51-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: [1-[2-(2-Diphenylphosphanylimidazol-1-yl)phenyl]imidazol-2-yl]-diphenylphosphane
• 英文别名: [1-[2-(2-diphenylphosphanylimidazol-1-yl)phenyl]imidazol-2-yl]-diphenylphosphane
• CAS: 1159579-51-7
• 化学式: C₃₆H₂₈N₄P₂
• 分子量: 578.593
• InChiKey: PSGOGVFCGULXDL-UHFFFAOYSA-N

物化性质

• 熔点：
  197-200 °C(Solvent: Dichloromethane; Ethyl acetate)
• 沸点：
  777.5±70.0 °C(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7.5
• 重原子数：
  42
• 可旋转键数：
  8
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  35.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  [1-[2-(2-Diphenylphosphanylimidazol-1-yl)phenyl]imidazol-2-yl]-diphenylphosphane 、 三氟甲烷磺酸甲酯 以 二氯甲烷 为溶剂， 反应 2.0h， 以70%的产率得到
  参考文献：
  名称：

  Flexible Diphosphine Ligands with Overall Charges of 0, +1, and +2: Critical Role of the Electrostatics in Favoring Trans over Cis Coordination

  摘要：

  The influence of the formal electrostatic interaction on the cis/trans coordination mode at a PdCl2 center is investigated in a family of isostructural flexible diphosphine ligands Ph2P-X-C6H4-Y-PPh2, where X and Y stand for neutral or cationic N,C-imidazolylene linkers. While the neutral and monocationic diphosphine spontaneously behave as classical cis-chelating ligands, only the dicationic diphosphine, where the electrostatic repulsion between the formal positive charges specifically takes place, is observed to behave as a trans-chelating ligand. The crucial role of electrostatics is analyzed on the basis of P-31 NMR data in solution and X-ray diffraction data in the crystal state. Comparative theoretical studies of the cis- and trans-chelated complexes, including EDA, static P-31 NMR, MESP, and AIM analyses, have been undertaken on the basis of DFT calculations in the gas phase or in the acetonitrile continuum. Whereas the cis-coordination mode is shown to be thermodynamically favored for the neutral ligand, the trans-coordination mode is found to be preferred for the dicationic homologue. The stereochemical preference is thus shown to be parallel to the expected effect of the formal electrostatic interaction. The results open perspectives for control of the cis- and trans-chelating behavior of flexible bidentate ligands by more or less reversible charge transfer at the periphery of the coordination sphere of a metallic center.

  DOI：

  10.1021/ic201342z

文献信息

• Flexible Diphosphine Ligands with Overall Charges of 0, +1, and +2: Critical Role of the Electrostatics in Favoring Trans over Cis Coordination
  作者：Yves Canac、Nathalie Debono、Christine Lepetit、Carine Duhayon、Remi Chauvin

  DOI：10.1021/ic201342z

  日期：2011.11.7

  The influence of the formal electrostatic interaction on the cis/trans coordination mode at a PdCl2 center is investigated in a family of isostructural flexible diphosphine ligands Ph2P-X-C6H4-Y-PPh2, where X and Y stand for neutral or cationic N,C-imidazolylene linkers. While the neutral and monocationic diphosphine spontaneously behave as classical cis-chelating ligands, only the dicationic diphosphine, where the electrostatic repulsion between the formal positive charges specifically takes place, is observed to behave as a trans-chelating ligand. The crucial role of electrostatics is analyzed on the basis of P-31 NMR data in solution and X-ray diffraction data in the crystal state. Comparative theoretical studies of the cis- and trans-chelated complexes, including EDA, static P-31 NMR, MESP, and AIM analyses, have been undertaken on the basis of DFT calculations in the gas phase or in the acetonitrile continuum. Whereas the cis-coordination mode is shown to be thermodynamically favored for the neutral ligand, the trans-coordination mode is found to be preferred for the dicationic homologue. The stereochemical preference is thus shown to be parallel to the expected effect of the formal electrostatic interaction. The results open perspectives for control of the cis- and trans-chelating behavior of flexible bidentate ligands by more or less reversible charge transfer at the periphery of the coordination sphere of a metallic center.