fac-(CO)3(1,3-bis(diphenylphosphino)propane)MnOTs | 148447-54-5

• 英文名称: fac-(CO)3(1,3-bis(diphenylphosphino)propane)MnOTs
• 英文别名: fac-[Mn(tosylato)(dppp)(CO)3]；fac-[Mn(tosylato)(1,3-bis(diphenylphosphino)propane)(CO)3]
• CAS: 148447-54-5
• 化学式: C₃₇H₃₃MnO₆P₂S
• 分子量: 722.617
• InChiKey: ISOPMWNLEWFRDK-UHFFFAOYSA-M

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(1,3-bis(diphenylphosphino)propane)MnOTs 、 sodium methylate 以 not given 为溶剂， 生成 fac-[Mn(OMe)(1,3-bis(diphenylphosphino)propane)(CO)3]
  参考文献：
  名称：

  Structural Characterization of Several (CO)₃(dppp)MnX Derivatives, dppp = 1,3-Bis(diphenylphosphino)propane and X = H, OTs, OC₂H₅, Cl, Br, or N₃. An Assessment of Their Efficacy for Catalyzing the Coupling of Carbon Dioxide and Epoxides

  摘要：

  The X-ray structures of a series of (CO)(3)(dppp)MnX complexes, X = H, OTs, OEt, Cl, Br, and N-3, and dppp = 1,3-bis(diphenylphosphino)propane, prepared by literature methods are reported. Several of these derivatives have been examined for their ability to serve as catalysts for the coupling of cyclohexene oxide and carbon dioxide. Although, these organometallic complexes do catalyze the formation of polycarbonate, their activity is not competitive with other very effective catalysts for this coupling reaction. Nevertheless, findings from these studies contribute significantly to our understanding of this important process. The complex containing the alkoxide ligand is the most active, yet it possesses a TON (mol epoxide consumed/mol Mn) of only 50 for a 24 h reaction. In this instance the (CO)(3)(dppp)MnOEt complex exists as the carbonate species, (CO)(3)(dppp)MnOC(O)OEt, because of rapid CO2 insertion into the Mn-OEt bond. The order of epoxide ring-opening by the X group (initiator) was found to be -OC(O)OR > Cl greater than or equal to N-3 > Br. Furthermore, since these complexes are substitutionally inert, this process is best defined as occurring via an associative interchange process and is rate-limiting.

  DOI：

  10.1021/om049352v
• 作为产物：
  描述：

  fac-tricarbonyl(1,3-bis(diphenylphosphino)propane)hydridomanganese(I) 、 对甲苯磺酸 以 二氯甲烷 为溶剂， 以91%的产率得到fac-(CO)3(1,3-bis(diphenylphosphino)propane)MnOTs
  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