[(C5Me5)Ir(η(5)-C6H3Me2O)]BF4 | 185139-51-9

• 分子结构分类: 有机化合物 - 碳氢化合物衍生物 - 环庚三烯酮
• 英文名称: [(C5Me5)Ir(η(5)-C6H3Me2O)]BF4
• 英文别名: 3,4-dimethylcyclohexa-2,5-dien-1-one;iridium(3+);1,2,3,4,5-pentamethylcyclopenta-1,3-diene;tetrafluoroborate
• CAS: 185139-51-9
• 化学式: BF₄*C₁₈H₂₄IrO
• 分子量: 535.413
• InChiKey: PVEIAHHQNFNUAY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 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：
  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：

  甲醇 、 [(C5Me5)Ir(η(5)-C6H3Me2O)]BF4 在 NaH 作用下， 以 甲醇 为溶剂， 以88%的产率得到(C5Me5)Ir(η(4)-C6H3Me2O(OMe))
  参考文献：
  名称：

  Regioselective Ortho-Functionalization of Phenols Promoted by the “Cp*Ir” Unit in [Cp*Ir(oxo-η⁵-cyclohexadienyl)][BF₄] Complexes

  摘要：

  A series of alkylated phenols (phenol, 3,5-dimethylphenol and 3,4-dimethylphenol) were complexed by the [Cp*Ir(solvent)(3)][BF4](2) (1) unit prepared in situ; subsequent treatment with NEt(3) produced the (oxo-eta(5)-cyclohexadienyl)iridium complexes [Cp*Ir(eta(5)-C(6)H(3)R(2)O)][BF4] [R = H (2); R = Me (3, 4)]. The X-ray molecular structure of 3 was determined. These (oxo-eta(5)-cyclohexadienyl)iridium derivatives react with NaOMe in methanol to give the novel iridium cyclohexadienone complexes [Cp*Ir{eta(4)-C(6)H(3)R(2)O(OMe)}] [R = H (5); R = Me (6, 7)] in 75-90% yield with nucleophilic attack occurring exclusively at the ortho-position relative to the C=O function. Addition of HBF4 . Me(2)O to these iridium cyclohexadienone complexes 5-7 affords the starting material (oxo-eta(5)-cyclohexadienyl)iridium derivatives 2-4 with MeOH. Further exposure to HBF4 . Me(2)O produces the corresponding phenolic compounds [Cp*Ir(eta(6)-C(6)H(3)R(2)OH)][BF4](2) (8 - 10); these chemical reactions are accompanied with hapticity changes eta(4) --> eta(5) --> eta(6) of the coordinated pi-hydrocarbon. The novel iridium cyclohexadienone complexes 5-7 can be oxidized easily by iodine to produce the free cyclohexadienones which rearomatize to give the free ortho-substituted phenols 11-13 in yields from 80% to quantitative.

  DOI：

  10.1021/om9606698
• 作为产物：
  描述：

  3,4-二甲基苯酚 、 bis[dichloro(pentamethylcyclopentadienyl)iridium(III)] 、 silver tetrafluoroborate 以 二氯甲烷 、 丙酮 为溶剂， 以86%的产率得到[(C5Me5)Ir(η(5)-C6H3Me2O)]BF4
  参考文献：
  名称：

  Regioselective Ortho-Functionalization of Phenols Promoted by the “Cp*Ir” Unit in [Cp*Ir(oxo-η⁵-cyclohexadienyl)][BF₄] Complexes

  摘要：

  A series of alkylated phenols (phenol, 3,5-dimethylphenol and 3,4-dimethylphenol) were complexed by the [Cp*Ir(solvent)(3)][BF4](2) (1) unit prepared in situ; subsequent treatment with NEt(3) produced the (oxo-eta(5)-cyclohexadienyl)iridium complexes [Cp*Ir(eta(5)-C(6)H(3)R(2)O)][BF4] [R = H (2); R = Me (3, 4)]. The X-ray molecular structure of 3 was determined. These (oxo-eta(5)-cyclohexadienyl)iridium derivatives react with NaOMe in methanol to give the novel iridium cyclohexadienone complexes [Cp*Ir{eta(4)-C(6)H(3)R(2)O(OMe)}] [R = H (5); R = Me (6, 7)] in 75-90% yield with nucleophilic attack occurring exclusively at the ortho-position relative to the C=O function. Addition of HBF4 . Me(2)O to these iridium cyclohexadienone complexes 5-7 affords the starting material (oxo-eta(5)-cyclohexadienyl)iridium derivatives 2-4 with MeOH. Further exposure to HBF4 . Me(2)O produces the corresponding phenolic compounds [Cp*Ir(eta(6)-C(6)H(3)R(2)OH)][BF4](2) (8 - 10); these chemical reactions are accompanied with hapticity changes eta(4) --> eta(5) --> eta(6) of the coordinated pi-hydrocarbon. The novel iridium cyclohexadienone complexes 5-7 can be oxidized easily by iodine to produce the free cyclohexadienones which rearomatize to give the free ortho-substituted phenols 11-13 in yields from 80% to quantitative.

  DOI：

  10.1021/om9606698