[Ir(CO)(PPh3)(η5-C5H3(SiMe3)2)] | 947586-55-2

• 英文名称: [Ir(CO)(PPh3)(η5-C5H3(SiMe3)2)]
• 英文别名: Ir(CO)(PPh3)(η5-1,2-bis(trimethylsilyl)cyclopentadienyl)
• CAS: 947586-55-2
• 化学式: C₃₀H₃₆IrOPSi₂
• 分子量: 691.98
• InChiKey: XPEXZUVGUNAEGQ-UHFFFAOYSA-N

反应信息

• 作为产物：
  描述：

  以 苯 为溶剂， 以93%的产率得到[Ir(CO)(PPh3)(η5-C5H3(SiMe3)2)]
  参考文献：
  名称：

  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

  摘要：

  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.

  DOI：

  10.1021/om700336d