[(Me5C5)Ir(2-tert-butylamino-4,6-di-tert-butylphenol(-2H))] | 1221689-45-7

• 英文名称: [(Me5C5)Ir(2-tert-butylamino-4,6-di-tert-butylphenol(-2H))]
• 英文别名: [Cp(*)Ir(2-tert-butylamino-4,6-di-tert-butylphenol(-2H))]
• CAS: 1221689-45-7
• 化学式: C₂₈H₄₄IrNO
• 分子量: 602.883
• InChiKey: HLWGMASBWCXLJY-UHFFFAOYSA-M

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：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  四氟硼酸-二乙醚络合物 、 [(Me5C5)Ir(2-tert-butylamino-4,6-di-tert-butylphenol(-2H))] 以 乙醚 为溶剂， 以84%的产率得到[(Me5C5)Ir(2-tert-butylamino-4,6-di-tert-butylphenol(-H))][BF4]
  参考文献：
  名称：

  含有非纯氨基酚盐的铱配合物的质子化增强路易斯酸度

  摘要：

  研究了非无辜配体的金属配合物质子化的影响。[H2tBAtBu = 2-叔丁基氨基-4,6-二叔丁基苯酚，H2tBAFPh = 2-(2-三氟甲基)氨基-4， 6-二叔丁基苯酚]。1 与 HBF4 的质子化得到苯胺酚盐 [1H]+。该复合物的晶体学表征揭示了拉长的 Ir-N 键，但 IrIII 中心保持五配位。苯胺苯酚氢化物 1H(H) 是通过用硼氢化物试剂和甲酸处理 [1H]+ 来制备的。X 射线晶体学证实了该结构，并揭示了氢化物和铵氢离子占据 IrONC6 环两侧的位置。复合物 2 仅被强酸质子化，并且所得衍生物在没有配体如CO和PMe3的情况下是不稳定的。[2(PMe3)]+ 的晶体学表征表明质子化发生在 O 而非 N。[2H]+ 的羰基化揭示了动力学加合物的中间性，这被认为是苯胺互变异构体。

  DOI：

  10.1002/ejic.201101011
• 作为产物：
  描述：

  bis[dichloro(pentamethylcyclopentadienyl)iridium(III)] 、 4,6-di-tert-butyl-N-(tert-butyl)-o-aminophenol 在 K₂CO₃ 、 (C₂H₅)4NCl 作用下， 以 二氯甲烷 为溶剂， 以75%的产率得到[(Me5C5)Ir(2-tert-butylamino-4,6-di-tert-butylphenol(-2H))]
  参考文献：
  名称：

  Oxidation of Dihydrogen by Iridium Complexes of Redox-Active Ligands

  摘要：

  Unsaturated organoiridium complexes were prepared with amidophenolate ligands derived from 2-(2-trifluoromethyl)amino-4,6-di-tert-butylphenol (H(2)(t)BA(F)) and 2-tert-butylamino-4,6-di-tert-butylphenol (H(2)(t)BA(tBu)). The following 16e complexes were characterized: Cp*M((t)BA(R)) with M = Ir (1(F) and 1(t-Bu)), Rh (2(F)), and (cymene)Ru((t)BA(F)) (3(F)). These complexes undergo two 1e oxidations at potentials of about 0 and -0.25 V vs Cp2Fe0/+. The magnitude of Delta E-1/2 is sensitive to the counteranions, and the reversibility is strongly affected by the presence of Lewis bases, which stabilize the oxidized derivatives. Crystallographic measurements indicate that upon oxidation the amidophenolate ligands adopt quinoid character, as indicated by increased alternation of the C C bond lengths in the phenylene ring backbone and shortened C-N and C-o bonds. Unlike the charge-neutral precursors, the cationic [Cp*M((t)BA(R))](+) are Lewis acidic and form well-characterized adducts with PR3 (R = Me, Ph), CN-, MeCN (reversibly), and CO. In the absence of competing ligands, the cations oxidize H-2. Coulommetry measurements indicate that H2 is oxidized by the monocations [Cp*M((t)BA(R))](+), not the corresponding dications. Oxidation of H-2 is catalytic in the presence of a noncoordinating base at potentials required for the generation of [Cp*M((t)BA(R))](+). The rate decreases in the order [Cp*M((t)BA(F))]BAr4F > [Cp*M((t)BA(F))]PF6 > [Cp*M((t)BA(t-Bu))]PF6. The reduction of ferrocenium by H-2 is catalyzed by Cp*M((t)BA(R)).

  DOI：

  10.1021/om9010593
• 作为试剂：
  描述：

  ferrocenium hexafluorophosphate 在 [(Me5C5)Ir(2-tert-butylamino-4,6-di-tert-butylphenol(-2H))] H₂ 、 2,6-di-tert-butylpyridine 作用下， 以 二氯甲烷 为溶剂， 生成 二茂铁
  参考文献：
  名称：

  Oxidation of Dihydrogen by Iridium Complexes of Redox-Active Ligands

  摘要：

  Unsaturated organoiridium complexes were prepared with amidophenolate ligands derived from 2-(2-trifluoromethyl)amino-4,6-di-tert-butylphenol (H(2)(t)BA(F)) and 2-tert-butylamino-4,6-di-tert-butylphenol (H(2)(t)BA(tBu)). The following 16e complexes were characterized: Cp*M((t)BA(R)) with M = Ir (1(F) and 1(t-Bu)), Rh (2(F)), and (cymene)Ru((t)BA(F)) (3(F)). These complexes undergo two 1e oxidations at potentials of about 0 and -0.25 V vs Cp2Fe0/+. The magnitude of Delta E-1/2 is sensitive to the counteranions, and the reversibility is strongly affected by the presence of Lewis bases, which stabilize the oxidized derivatives. Crystallographic measurements indicate that upon oxidation the amidophenolate ligands adopt quinoid character, as indicated by increased alternation of the C C bond lengths in the phenylene ring backbone and shortened C-N and C-o bonds. Unlike the charge-neutral precursors, the cationic [Cp*M((t)BA(R))](+) are Lewis acidic and form well-characterized adducts with PR3 (R = Me, Ph), CN-, MeCN (reversibly), and CO. In the absence of competing ligands, the cations oxidize H-2. Coulommetry measurements indicate that H2 is oxidized by the monocations [Cp*M((t)BA(R))](+), not the corresponding dications. Oxidation of H-2 is catalytic in the presence of a noncoordinating base at potentials required for the generation of [Cp*M((t)BA(R))](+). The rate decreases in the order [Cp*M((t)BA(F))]BAr4F > [Cp*M((t)BA(F))]PF6 > [Cp*M((t)BA(t-Bu))]PF6. The reduction of ferrocenium by H-2 is catalyzed by Cp*M((t)BA(R)).

  DOI：

  10.1021/om9010593