[(p-cymene)Ru(2-(2-trifluoromethyl)amino-4,6-di-tert-butylphenol(-2H))] | 1221689-44-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [(p-cymene)Ru(2-(2-trifluoromethyl)amino-4,6-di-tert-butylphenol(-2H))]
• 英文别名: 2,4-Ditert-butyl-6-[2-(trifluoromethyl)phenyl]azanidylphenolate;1-methyl-4-propan-2-ylbenzene;ruthenium(2+)
• CAS: 1221689-44-6
• 化学式: C₃₁H₃₈F₃NORu
• 分子量: 598.714
• InChiKey: YHPZHZFTQQKIPH-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  9.83
• 重原子数：
  37
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  24.1
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  ferrocenium hexafluorophosphate 、 [(p-cymene)Ru(2-(2-trifluoromethyl)amino-4,6-di-tert-butylphenol(-2H))] 以 二氯甲烷 为溶剂， 以70%的产率得到[(p-cymene)Ru(2-(2-trifluoromethyl)amino-4,6-di-tert-butylphenol(-2H))]PF6
  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
• 作为产物：
  描述：

  2-(2-trifluoromethyl)anilino-4,6-di-tert-butylphenol 、 [ruthenium(II)(η⁶-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]₂ 在 (C₂H₅)3N 作用下， 以 乙腈 为溶剂， 以87%的产率得到[(p-cymene)Ru(2-(2-trifluoromethyl)amino-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