IrCl(CO)[P(i-Bu)3]2 | 591249-01-3

• 英文名称: IrCl(CO)[P(i-Bu)3]2
• CAS: 591249-01-3
• 化学式: C₂₅H₅₄ClIrOP₂
• 分子量: 660.324
• InChiKey: GWXGIZQASYJSMC-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：

  IrCl(CO)[P(i-Bu)3]2 在 氢气 作用下， 以 甲苯 为溶剂， 生成
  参考文献：
  名称：

  Wilson, Matthew R.; Liu, Hongye; Prock, Alfred, Organometallics, 1993, vol. 12, # 6, p. 2044 - 2050

  摘要：

  DOI：

文献信息

• Synthesis, Spectroscopy, and Structure of a Family of Iridabenzenes Generated by the Reaction of Vaska-Type Complexes with a Nucleophilic 3-Vinyl-1-cyclopropene
  作者：Robert D. Gilbertson、Thomas L. S. Lau、Seren Lanza、He-Ping Wu、Timothy J. R. Weakley、Michael M. Haley

  DOI：10.1021/om030394d

  日期：2003.8.1

  Seven new iridabenzenes were prepared by the addition of (Z)-1,2-diphenyl-3-(2-lithioethenyl)-1-cyclopropene to the Vaska-type complexes [IrCl(CO)(PR3)2], containing differing phosphine ligands. The iridabenzenes could be isolated from the reaction mixture either by direct means or after heating of the crude solution. In the case of the reactions using PMe3 and PEt3, a σ-vinyl/η2-cyclopropene Ir(I)

  通过在Vaska型络合物[IrCl（CO）（PR 3）2 ]中添加（Z）-1,2-二苯基-3-（2-硫代乙烯基）-1-环丙烯，制备了七个新的铱膦配体。可以通过直接方式或在加热粗溶液后从反应混合物中分离出铱苯。在使用PME的反应的情况下3和宠物3，一个σ乙烯基/η 2 -环丙烯的Ir（I）络合物，最好描述为一个iridabenzvalene，可以分离和完全表征。通过在溶液中加热，金属戊二烯中间体可以干净地转化为相应的铱苯。PEt 3用X射线晶体学表征取代的铱苯和iridabenzvalene。假定了从锂化的乙烯基环丙烯形成两个iridacycles以及将苯并戊烯异构化为苯的合理机理。
• 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.