| 63816-44-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• CAS: 63816-44-4
• 化学式: C₃₇H₆₆NiO₄P₂
• 分子量: 695.566
• InChiKey: IPUXMLGGKKTKGS-UHFFFAOYSA-L

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：

  以 neat (no solvent) 为溶剂， 生成
  参考文献：
  名称：

  Mechanism of formation of the peroxocarbonate complex (PCy3)2Ni(CO4) from solid (PCy3)2Ni(CO2) and dioxygen: an example of solid-state metallorganic reaction involving CO2 deco-ordination and reinsertion into the OO bond of (PCy3)2Ni(O2). Reactivity of the peroxocarbonate complex towards olefins in the solid state and in solution

  摘要：

  Solid (PCY3)(2)Ni(CO2) (1) reacts with dioxygen to afford the peroxocarbonate Complex (PCY3)(2)Ni(CO2) (3). The use of labelled (CO2)-C-13, (CO2-)-O-18 O-18(2), coupled with a FTIR study of both the gas-phase in equilibrium with the solid and the solid resulting complex, allows to propose the reaction mechanism that implies CO2 deco-ordination, O-2, co-ordination, and CO2 insertion into the O-O bond of the newly formed, reactive (PCy3)(2)Ni(O-2) complex 2. A normal mode analysis substantiates the band assignment and the proposed mechanism. Peroxocarbonate (3) exhibits a C-13 resonance at 166.6 ppm and a single P-31 signal at 43.1 ppm below 200 K. The reactivity of the peroxo-group as one-oxygen transfer agent prevents the spectroscopic characterisation of 3 in solution at room temperature. An out-of-sphere phosphine can be easily oxidised. A gaseous olefin. mono-ene (ethylene) or diene (allene), added to 3. makes easier the deco-ordination process of one phosphine ligand, that is then oxidised to phosphine oxide. The gaseous olefin itself is not oxidised until free phosphine is present in the medium. In solution, styrene is oxidised through a two or one-oxygen transfer pathway, according to the reaction condition. (C) 2002 Published by Elsevier Science.

  DOI：

  10.1016/s0020-1693(01)00737-x
• 作为产物：
  描述：

  氧气 、 (carbon dioxide)bis(tricyclohexylphosphine)nickel 以 neat (no solvent) 为溶剂， 生成 二氧化碳 、
  参考文献：
  名称：

  Mechanism of formation of the peroxocarbonate complex (PCy3)2Ni(CO4) from solid (PCy3)2Ni(CO2) and dioxygen: an example of solid-state metallorganic reaction involving CO2 deco-ordination and reinsertion into the OO bond of (PCy3)2Ni(O2). Reactivity of the peroxocarbonate complex towards olefins in the solid state and in solution

  摘要：

  Solid (PCY3)(2)Ni(CO2) (1) reacts with dioxygen to afford the peroxocarbonate Complex (PCY3)(2)Ni(CO2) (3). The use of labelled (CO2)-C-13, (CO2-)-O-18 O-18(2), coupled with a FTIR study of both the gas-phase in equilibrium with the solid and the solid resulting complex, allows to propose the reaction mechanism that implies CO2 deco-ordination, O-2, co-ordination, and CO2 insertion into the O-O bond of the newly formed, reactive (PCy3)(2)Ni(O-2) complex 2. A normal mode analysis substantiates the band assignment and the proposed mechanism. Peroxocarbonate (3) exhibits a C-13 resonance at 166.6 ppm and a single P-31 signal at 43.1 ppm below 200 K. The reactivity of the peroxo-group as one-oxygen transfer agent prevents the spectroscopic characterisation of 3 in solution at room temperature. An out-of-sphere phosphine can be easily oxidised. A gaseous olefin. mono-ene (ethylene) or diene (allene), added to 3. makes easier the deco-ordination process of one phosphine ligand, that is then oxidised to phosphine oxide. The gaseous olefin itself is not oxidised until free phosphine is present in the medium. In solution, styrene is oxidised through a two or one-oxygen transfer pathway, according to the reaction condition. (C) 2002 Published by Elsevier Science.

  DOI：

  10.1016/s0020-1693(01)00737-x