| 147311-40-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• CAS: 147311-40-8
• 化学式: C₁₁H₂₅IrO₂P₂
• 分子量: 443.486
• InChiKey: QRSWUYUKERPRTO-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

• 作为反应物：
  描述：

  、 3-deutro-1,2-diphenyl-3-vinyl-1-cyclopropene 以 氘代苯 为溶剂， 生成 cis-acetylacetonato(1,5-η-3-deutero-1,2-diphenyl-1,3-pentadienediyl)bis(trimethylphosphine)iridium(III)
  参考文献：
  名称：

  Iridium-Promoted Reactions of Carbon−Carbon Bonds. Skeletal Rearrangement of a Vinylcyclopropene during Iridacyclohexadiene Formation and Subsequent Isomerization of Iridacyclohexadienes via α,α‘-Substituent Migrations

  摘要：

  On treatment with [Ir(PMe3)(2)(acac)] at room temperature, 1,2,3-triphenyl-3-vinylcyclopropene undergoes ring opening accompanied by rearrangement to give, instead of the expected 1,2,3-triphenyliridacyclohexadiene complex, a crystallographically characterized 1,2,4-triphenyliridacyclohexadiene complex containing cis-phosphine ligands. Studies with H-2- and doubly C-13-labeled vinylcyclopropenes, the syntheses and characterization of which are also reported, show that this process involves a rearrangement of the carbon skeleton and not a substituent shift. The corresponding 1,2-diphenyl-3-vinylcyclopropene undergoes iridacyclohexadiene formation without any rearrangement. On heating at 90 degrees C, each iridacycle converts to its corresponding isomer containing trans-phosphine ligands without any skeletal or substituent rearrangement of the metallacycle, as evidenced by absence of change in the labeling pattern. At higher temperatures, further rearrangement occurs in the case of each metallacycle, which does not alter the metallacyclohexadiene backbone, but rather exchanges the substituents of the alpha and alpha' carbon atoms. This rearrangement is shown to occur even when there is no driving force due to relief of steric effects. Mechanisms for each rearrangement are proposed and discussed.

  DOI：

  10.1021/ja992407d
• 作为产物：
  描述：

  diμ-chlorotetrakis(η2-cyclooctene)diiridium(I) 、 thallium(I) 2,4-pentanedionate 、 三甲基膦 以 二氯甲烷 为溶剂， 以78%的产率得到
  参考文献：
  名称：

  Iridium-Promoted Reactions of Carbon−Carbon Bonds. Skeletal Rearrangement of a Vinylcyclopropene during Iridacyclohexadiene Formation and Subsequent Isomerization of Iridacyclohexadienes via α,α‘-Substituent Migrations

  摘要：

  On treatment with [Ir(PMe3)(2)(acac)] at room temperature, 1,2,3-triphenyl-3-vinylcyclopropene undergoes ring opening accompanied by rearrangement to give, instead of the expected 1,2,3-triphenyliridacyclohexadiene complex, a crystallographically characterized 1,2,4-triphenyliridacyclohexadiene complex containing cis-phosphine ligands. Studies with H-2- and doubly C-13-labeled vinylcyclopropenes, the syntheses and characterization of which are also reported, show that this process involves a rearrangement of the carbon skeleton and not a substituent shift. The corresponding 1,2-diphenyl-3-vinylcyclopropene undergoes iridacyclohexadiene formation without any rearrangement. On heating at 90 degrees C, each iridacycle converts to its corresponding isomer containing trans-phosphine ligands without any skeletal or substituent rearrangement of the metallacycle, as evidenced by absence of change in the labeling pattern. At higher temperatures, further rearrangement occurs in the case of each metallacycle, which does not alter the metallacyclohexadiene backbone, but rather exchanges the substituents of the alpha and alpha' carbon atoms. This rearrangement is shown to occur even when there is no driving force due to relief of steric effects. Mechanisms for each rearrangement are proposed and discussed.

  DOI：

  10.1021/ja992407d