[Ir(CO)(PPh3)(η5-C5H3Ph(SiMe3))] | 445263-22-9

• 英文名称: [Ir(CO)(PPh3)(η5-C5H3Ph(SiMe3))]
• CAS: 445263-22-9
• 化学式: C₃₃H₃₂IrOPSi
• 分子量: 695.896
• InChiKey: QVJXVEOBBGZTNZ-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：

  以 氘代苯 为溶剂， 以89%的产率得到[Ir(CO)(PPh3)(η5-C5H3Ph(SiMe3))]
  参考文献：
  名称：

  Metallabenzenes and Valence Isomers. 3. Unexpected Rearrangement of Two Regioisomeric Iridabenzenes to an (η⁵-Cyclopentadienyl)iridium(I) Complex

  摘要：

  The reaction of (Z)-1-phenyl-2-(trimethylsilyl)-3-(2-lithiovinyl)cyclopropene (4) with Vaska's complex generates the iridabenzvalene 8, the iridabenzene 9, and the cyclopentadienyl complex 10 in a 10:2:3 ratio. Heating this mixture to 75 degreesC converts 8 and 9 to 10. NMR studies over a 24 h period at 75 degreesC show that samples containing pure 8 isomerize to 10 in high yield and generate regioisomeric iridabenzene 11 as an intermediate.

  DOI：

  10.1021/om0201563

文献信息

• Rearrangement of Iridabenzvalenes to Iridabenzenes and/or η⁵-Cyclopentadienyliridium(I) Complexes:  Experimental and Computational Analysis of the Influence of Silyl Ring Substituents and Phosphine Ligands
  作者：He-Ping Wu、Daniel H. Ess、Seren Lanza、Timothy J. R. Weakley、K. N. Houk、Kim K. Baldridge、Michael M. Haley

  DOI：10.1021/om700336d

  日期：2007.7.30

  Lithium-halogen exchange of either (Z)-1-phenyl-2-trimethylsilyl- (5a) or (Z)-1,2-bis(trimethylsilyl)-3-(2-iodovinyl)cyclopropene (5b) and addition to either Vaska's or Vaska-type complexes generated iridabenzvalenes (9, 14, 17), iridabenzenes (10, 18), and/or cyclopentadienyl complexes (11, 15, 19), depending on both the substituents on the C-5 framework and the phosphine ligands on Ir. Specifically, the reaction of 5awith Vaska's complex afforded a mixture of 9, 10, and 11. Heating this mixture to 75 degrees C converted 9 and 10 to 11. NMR studies at 75 degrees C showed that samples of 9 isomerize to 11 in high yield and generate regioisomeric iridabenzene 12 as an intermediate. The reaction of 5b with Vaska's complex produced benzvalene 14 as the sole product. Complex 14 transformed completely to cyclopentadienyliridium complex 15 at 75 degrees C with no benzene intermediate detectable by NMR spectroscopy. The reaction of cyclopropene 5a with Vaska-type complexes containing alkylphosphines of varying cone angles yielded only benzvalene complexes, which either rearranged or decomposed depending upon the extent of heating. A hybrid-DFT computational study was carried out to investigate reactivity differences between phenyl and trimethylsilyl iridabenzvalenes, regioselective rearrangement of 9, and the unexpected stability/instability of 14/16. These calculations rationalize the sometimes contradictory experimental results.