fac-Mn(CO)3(1,3-bis(diphenylphosphino)propane)(N3) | 191719-65-0

• 英文名称: fac-Mn(CO)3(1,3-bis(diphenylphosphino)propane)(N3)
• 英文别名: fac-[Mn(N3)(dppp)(CO)3]；fac-[Mn(N3)(1,3-bis(diphenylphosphino)propane)(CO)3]
• CAS: 191719-65-0
• 化学式: C₃₀H₂₆MnN₃O₃P₂
• 分子量: 593.44
• InChiKey: BRGDASNNTZZBIV-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

• 作为产物：
  描述：

  fac-Mn(CO)3(1,3-bis(diphenylphosphino)propane)Br 、 sodium azide 以 甲醇 为溶剂， 生成 fac-Mn(CO)3(1,3-bis(diphenylphosphino)propane)(N3)
  参考文献：
  名称：

  fac-（CO）3（PP）Mn-Z配合物的制备，反应和红外光谱（PP = DEPE，DPPE，DPPP; Z = H，OTs，OMe，OC（O）OMe，NCO，Cl，Br， N 3）

  摘要：

  一系列新的八面体Mn（I）配合物fac-（CO）3（depe）Mn-Z（depe = 1,2-双（二乙基膦基）乙烷，Z = H，OTs，OMe，OC（O）OMe，NCO ，Cl，Br，N 3）已经被制备和表征，特别是关于它们的红外光谱。与配位的一氧化碳有关的羰基拉伸频率中观察到的变化是Z基团的函数。这些光谱与类似的dppp，1，3-双（二苯基膦基）丙烷和dppe，1，2-双（二苯基膦基）乙烷络合物的相似光谱的比较显示了用苯基取代磷原子上的乙基的效果。Depe叠氮基络合物（Z = N 3）与炔烃反应生成三唑并合物，在与HCl水解后释放出三唑并再生生成叠氮基的氯配合物。

  DOI：

  10.1016/s0022-328x(97)00043-0

文献信息

• 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
  作者：Donald J. Darensbourg、Poulomi Ganguly、Damon R. Billodeaux

  DOI：10.1021/om049352v

  日期：2004.12.1

  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.