dimethyl(η5-indenyl)(trimethylphosphine)iridium | 139377-84-7

• 英文名称: dimethyl(η5-indenyl)(trimethylphosphine)iridium
• CAS: 139377-84-7
• 化学式: C₁₄H₂₂IrP
• 分子量: 413.522
• InChiKey: BHESJMGUIGDERJ-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

• 作为反应物：
  描述：

  dimethyl(η5-indenyl)(trimethylphosphine)iridium 在 一氧化碳 作用下， 以 乙醚 为溶剂， 以96%的产率得到
  参考文献：
  名称：

  Migratory insertion reactions of indenyliridium dialkyls and alkyl and aryl hydrides

  摘要：

  This paper reports the migratory insertion chemistry of indenyliridium complexes described in the companion paper. Complexes of general formula (eta-5-Ind)(PMe3)Ir(R)(R'), where R = alkyl or aryl and R' = alkyl, aryl, or hydride (4-6) react with dative ligands L such as tert-butylisocyanide and CO. These transformations lead to eta-5 to eta-1 isomerization of the indenyl ligand, giving octahedral iridium complexes of general formula (eta-1-Ind)(PMe3)(L)2Ir(R)(R') (8, 9, 11). Treatment of the methyl aryl and dimethyl eta-1-indenyl complexes 9a, 9d, and 9e with trimethylamine oxide removes CO, allowing the indenyl ligand to reestablish eta-5-coordination by inducing CO migratory insertion to give acyl complexes 10. Reaction of eta-1-indenyl aryl and methyl hydrides 6 (as well as the dihydride (eta-5-Ind)(PMe3)IrH2 (7)) with CO leads to reductive elimination of arene, methane, or H-2 rather than migratory insertion, forming (eta-1-Ind)(CO)3(PMe3)Ir (12) as the organometallic product. In contrast, treatment of methyl and aryl hydrides 6 with alkynes leads to the methyl vinyl complexes (eta-5-Ind)(PMe3)Ir(Me)(CR=C(R')(H)) (13) and reaction of 6a with ethylene gives the methyl ethyl complex (eta-5-Ind)(PMe3)Ir(Me)(Et) (14). Isotope labeling, stereochemical, and kinetic studies have been carried out on the insertion reaction of 6a with 3,3-di-methyl-1-butyne. The results of these experiments are most consistent with a mechanism involving initial reversible coordination of alkyne to the metal center (probably with concurrent eta-5-eta-3 isomerization of the indenyl ligand) followed by irreversible migration of the metal-bound hydrogen to the tert-butyl-substituted carbon of the alkyne and then rapid recoordination of the indenyl group.

  DOI：

  10.1021/om00041a014
• 作为产物：
  描述：

  在 CH₃MgBr 作用下， 以 乙醚 、 甲苯 为溶剂， 以42%的产率得到dimethyl(η5-indenyl)(trimethylphosphine)iridium
  参考文献：
  名称：

  Foo, Thomas; Bergman, Robert G., Organometallics, 1992, vol. 11, # 5, p. 1801 - 1810

  摘要：

  DOI：