(η5-C5H5)Mn(CO)2(η2-C,C-2,3-dihydrofuran) | 1181253-67-7

• 英文名称: (η5-C5H5)Mn(CO)2(η2-C,C-2,3-dihydrofuran)
• 英文别名: CpMn(CO)2(η2-C,C-2,3-DHF)；(η6-C5H5)Mn(CO)2(η2-2,3-dihydrofuran)；CpMn(CO)2(η2-DHF)
• CAS: 1181253-67-7
• 化学式: C₁₁H₁₁MnO₃
• 分子量: 246.145
• InChiKey: RAHQOIULVJTWTQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  2,3-二氢呋喃 、 三羰基(η-环戊二烯基)合锰 以 further solvent(s) 为溶剂， 生成 (η5-C5H5)Mn(CO)2(η2-C,C-2,3-dihydrofuran)
  参考文献：
  名称：

  Linkage Isomerization Reactions of M(CO)₂L Complexes (M = (η⁵-C₅H₅)Mn, (η⁵-C₅H₅)Re, or (η⁶-C₆H₆)Cr; L = 2,3-Dihydrofuran): A Step-Scan FTIR and DFT Study

  摘要：

  The linkage isomers, M(CO)(2)-(eta(1)-(O)-2,3 DHF) and M(CO)(2)-(eta(2)-(C,C)-2,3 DHF) [M = (eta(5)-C5H5)Mn, (eta(5)-C5H5)Re, (eta(6)-C6H6)Cr; DHF = dihydrofuran] are formed upon photolysis of the parent M(CO)(3) complexes in the presence of 2,3-DHF. The rearrangement of the oxygen bound to the thermodynamically favored a bound complex is followed on the millisecond to microsecond time scale using step-scan FTIR. The rate of the isomerization reaction increases in the order Re < Mn < Cr primarily due to a decrease in the activation enthalpy. The experimental data along with theoretical calculations suggest that the rearrangement proceeds intramolecularly in which the metal migrates from one functional group to another.

  DOI：

  10.1021/om800457d

文献信息

• Displacement Kinetics of η²-Bound Furan and 2,3-Dihydrofuran from Mn and Cr Centers: Evidence for the Partial Dearomatization of the Furan Ligand
  作者：Jeremy R. Andreatta、G. Benjamin Cieslinski、Madeeha Batool、Xue-Zhong Sun、Michael W. George、Edward N. Brothers、Donald J. Darensbourg、Ashfaq A. Bengali

  DOI：10.1021/ic900724f

  日期：2009.8.17

  The displacement of eta(2)-coordinated ligands from the photolytically generated CpMn(CO)(2)L and BzCr(CO)(2)L [Cp = eta(5)-C5H5, Bz = eta(6)-C6H6, L =2,3-dihydrofuran (DHF), furan] complexes by pyridine has been studied. The displacement reactions span a wide range of time scales from microseconds to hours and were studied using a range of time-resolved IR spectroscopic techniques. The substitution reactions follow a dissociative pathway and the measured activation enthalpies provide an estimate for the strength of the metal-(eta(2)-furan) and metal-(eta(2)-DHF) interactions. In these complexes, the Cr center binds both ligands weaker than the Mn center, There is a similar to 6-10 kcal/mol difference in the binding enthalpies of eta(2)-furan and eta(2)-DHF to both metals suggesting that this difference is the result of a partial loss of resonance energy in the case of the aromatic furan ligand upon interaction with the metal.