(C5Me5)Ir(2-(2-trifluoromethylanilino-4,6-di-tert-butylphenol(2-)) | 1008364-25-7

• 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: (C5Me5)Ir(2-(2-trifluoromethylanilino-4,6-di-tert-butylphenol(2-))
• 英文别名: [Cp(*)Ir(2-(2-trifluoromethyl)amino-4,6-di-tert-butylphenol(-2H))]；2,4-ditert-butyl-6-[2-(trifluoromethyl)phenyl]azanidylphenolate;iridium(3+);1,2,3,4,5-pentamethylcyclopenta-1,3-diene
• CAS: 1008364-25-7
• 化学式: C₃₁H₃₉F₃IrNO
• 分子量: 690.872
• InChiKey: KJBMRPYMYUASAD-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  9.66
• 重原子数：
  37
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  24.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  六氟磷酸银 、 (C5Me5)Ir(2-(2-trifluoromethylanilino-4,6-di-tert-butylphenol(2-)) 以 二氯甲烷 为溶剂， 生成 [(C5Me5)Ir(2-(2-trifluoromethylanilino-4,6-di-tert-butylphenol(2-))]PF6
  参考文献：
  名称：

  Redox-Switched Oxidation of Dihydrogen Using a Non-Innocent Ligand

  摘要：

  Organometallic complexes containing non-innocent ligands of the type Cp*lr((t)BA(F)Ph))(1), where H2(t)BA(F)Ph is 2-(2-trifluoromethyl)anilino-4,6-di-tert-butophenol, were found to activate H-2 in a redox-switchable manner. The 16e(-) complex 1 was inert with respect to H-2, CO, as well as conventional basic substrates until oxidation. Oxidation of 16-electron 1 with 1 equiv of Ag+ resulted in ligand-centered oxidation affording salts of [1](+), which were characterized by crystallographically, EPR, and elemental analyses. [1](+) was reduced to 1 in the presence of H-2 and the sterically hindered base, 2,6-(Bu-t)(2)C5H3N, via a pathway that is first-order in both metal and dihydrogen. Compound [1](+) forms adducts; with MeCN, which inhibits catalysis. The catalytic oxidation of H2 was established by electrochemical methods to be associated with the monocation.

  DOI：

  10.1021/ja076801k
• 作为产物：
  描述：

  [(C5Me5)Ir(2-(2-trifluoromethylanilino-4,6-di-tert-butylphenol(2-))]PF6 以 乙腈 为溶剂， 生成 (C5Me5)Ir(2-(2-trifluoromethylanilino-4,6-di-tert-butylphenol(2-))
  参考文献：
  名称：

  Redox-Switched Oxidation of Dihydrogen Using a Non-Innocent Ligand

  摘要：

  Organometallic complexes containing non-innocent ligands of the type Cp*lr((t)BA(F)Ph))(1), where H2(t)BA(F)Ph is 2-(2-trifluoromethyl)anilino-4,6-di-tert-butophenol, were found to activate H-2 in a redox-switchable manner. The 16e(-) complex 1 was inert with respect to H-2, CO, as well as conventional basic substrates until oxidation. Oxidation of 16-electron 1 with 1 equiv of Ag+ resulted in ligand-centered oxidation affording salts of [1](+), which were characterized by crystallographically, EPR, and elemental analyses. [1](+) was reduced to 1 in the presence of H-2 and the sterically hindered base, 2,6-(Bu-t)(2)C5H3N, via a pathway that is first-order in both metal and dihydrogen. Compound [1](+) forms adducts; with MeCN, which inhibits catalysis. The catalytic oxidation of H2 was established by electrochemical methods to be associated with the monocation.

  DOI：

  10.1021/ja076801k

文献信息

• Oxidation of Dihydrogen by Iridium Complexes of Redox-Active Ligands
  作者：Mark R. Ringenberg、Mark J. Nilges、Thomas B. Rauchfuss、Scott R. Wilson

  DOI：10.1021/om9010593

  日期：2010.4.26

  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)).