fac-(CO)3(1,2-bis(diphenylphosphino)ethane)MnOCH2CF3 | 148447-57-8

• 英文名称: fac-(CO)3(1,2-bis(diphenylphosphino)ethane)MnOCH2CF3
• 英文别名: fac-Mn(CO)3(1,2-bis(diphenylphosphanyl)ethane)(OCH2CF3)
• CAS: 148447-57-8
• 化学式: C₃₁H₂₆F₃MnO₄P₂
• 分子量: 636.426
• InChiKey: VHUXSLPZWXRNSX-UHFFFAOYSA-N

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：

  fac-(CO)3(1,2-bis(diphenylphosphino)ethane)MnOCH2CF3 在 CO₂ 作用下， 以 苯 为溶剂， 以10%的产率得到fac-(CO)3(1,2-bis(diphenylphosphino)ethane)MnOC(O)OCH2CF3
  参考文献：
  名称：

  亲电试剂与锰（I）和rh（I）醇盐配合物的反应：大气二氧化碳的可逆吸收

  摘要：

  The transition metal alkoxides fac-(CO)3(P-P)MOR [where M is Mn or Re, P-P is either 1,2-bis(diphenylphosphino)ethane (dppe) or 1,3-bis(diphenylphosphino)propane (dppp), and R is either CH3, C2H5, or CF3CH2] react readily at room temperature with CO2, CS2, and PhNCO by insertion of these electrophiles into the metal-oxygen bond. The reactions with C02 leading to the corresponding carbonato complexes fac-(CO)3(P-P)MOC(O)OR are of special interest; benzene solutions of the alkoxides can even absorb CO2 from the atmosphere. All the carbonato complexes release C02 When argon is bubbled through solutions of them, regenerating the alkoxides. These equilibrium reactions make it possible to exchange the C02 of the carbonato complexes by treatment of them with CS2 or PhNCO. Only the C02 reaction is reversible under mild conditions. When a solution of fac-(CO)3(dppe)MnOC(O)OCH3 is treated with CH3NH2 followed by CO2 the metallourethane complex (CO)3(dppe)MnOC(O)NHCH3 is formed. The X-ray crystal structure of fac-(CO)3(dppe)MnOC(O)OCH3 is presented.

  DOI：

  10.1021/om00029a032
• 作为产物：
  描述：

  fac-(CO)3(1,2-bis(diphenylphosphino)ethane)Mn-p-toluenesulfonate 、 2,2,2-三氟乙醇 、 2,2,2-三氟乙醇钠 以 neat (no solvent) 为溶剂， 以77%的产率得到fac-(CO)3(1,2-bis(diphenylphosphino)ethane)MnOCH2CF3
  参考文献：
  名称：

  亲电试剂与锰（I）和rh（I）醇盐配合物的反应：大气二氧化碳的可逆吸收

  摘要：

  The transition metal alkoxides fac-(CO)3(P-P)MOR [where M is Mn or Re, P-P is either 1,2-bis(diphenylphosphino)ethane (dppe) or 1,3-bis(diphenylphosphino)propane (dppp), and R is either CH3, C2H5, or CF3CH2] react readily at room temperature with CO2, CS2, and PhNCO by insertion of these electrophiles into the metal-oxygen bond. The reactions with C02 leading to the corresponding carbonato complexes fac-(CO)3(P-P)MOC(O)OR are of special interest; benzene solutions of the alkoxides can even absorb CO2 from the atmosphere. All the carbonato complexes release C02 When argon is bubbled through solutions of them, regenerating the alkoxides. These equilibrium reactions make it possible to exchange the C02 of the carbonato complexes by treatment of them with CS2 or PhNCO. Only the C02 reaction is reversible under mild conditions. When a solution of fac-(CO)3(dppe)MnOC(O)OCH3 is treated with CH3NH2 followed by CO2 the metallourethane complex (CO)3(dppe)MnOC(O)NHCH3 is formed. The X-ray crystal structure of fac-(CO)3(dppe)MnOC(O)OCH3 is presented.

  DOI：

  10.1021/om00029a032

文献信息

• Kinetic Study of the Insertion and Deinsertion of Carbon Dioxide into <i>f</i><i>ac</i>-(CO)₃(dppe)MnOR Derivatives
  作者：Donald J. Darensbourg、Way-Zen Lee、Andrea L. Phelps、Erin Guidry

  DOI：10.1021/om034087j

  日期：2003.12.1

  The insertion of carbon dioxide into the Mn-O bond of fac-(CO)(3)(dppe)MnOCH3 (1) was observed to occur instantaneously at -78 degreesC by in situ infrared spectroscopy. The product of carboxylation of 1, fac-(CO)(3)(dppe)MnOC(O)OCH3 (2), underwent decarboxylation with a first-order rate constant of 1.49 x 10(-4) s(-1) at 23 degreesC. The kinetic parameters for this process were determined by trapping the intermediate produced upon CO2 extrusion, complex 1, with COS to provide the very stable fac-(CO)(3)(dppe)MnSC(O)OCH3 (3) derivative. The structure of 3 was determined by single-crystal X-ray diffraction analysis, establishing the presence of the Mn-S bond.