[Cp*Ir(H){κ2(N,C)-NH2C(C6H5)2-2-C6H4}] | 1027606-81-0

• 英文名称: [Cp*Ir(H){κ2(N,C)-NH2C(C6H5)2-2-C6H4}]
• 英文别名: [Cp*Ir(H){κ₂(N,C)-NH₂C(C₆H₅)₂-2-C₆H₄}]；Cp(*)IrH(H2NCPh2C6H4)
• CAS: 1027606-81-0
• 化学式: C₂₉H₃₂IrN
• 分子量: 586.8
• InChiKey: HDNWTYWHKNIEHQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• 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：

  [Cp*Ir(H){κ2(N,C)-NH2C(C6H5)2-2-C6H4}] 在 air 作用下， 以 氘代四氢呋喃 为溶剂， 生成 (1,2,3,4,5-pentamethylcyclopentadienyl)Ir-[κ²(N,C)-(NHC(C₆H₅₎₂-2-C₆H₄)]
  参考文献：
  名称：

  外消旋仲醇与手性双官能酰胺配合物的有氧氧化动力学拆分。

  摘要：

  DOI：

  10.1002/anie.200705875
• 作为产物：
  描述：

  [Cp*Ir(NCCH₃){κ₂(N,C)-(NH₂C(C₆H₅)₂-2-C₆H₄)}](SbF₆) 、 氢气 在 三乙胺 作用下， 以 氘代四氢呋喃 为溶剂， 反应 0.33h， 以100%的产率得到[Cp*Ir(H){κ2(N,C)-NH2C(C6H5)2-2-C6H4}]
  参考文献：
  名称：

  阳离子铱和铑配合物与C–N螯合伯胺基胺配体作为不饱和碳氮键加氢的有效催化剂

  摘要：

  Cationic half-sandwich C-N chelating Ir and Rh complexes [Cp*M(NCCH3){kappa(2)(N,C)-NH2CR2-2-C6H4}]+SbF6- (1a, M = Ir, R = CH3; 1b, M = Ir, R = C6H5; 2a, M = Rh, R = CH3; 2b, M = Rh, R = C6H5) are synthesized by AgSbF6-mediated halide abstraction from neutral azametallacycles derived from tritylamine or cumylamine and are fully characterized by NMR spectroscopy and X-ray crystallography. The treatment of the cationic complex 1b with H-2 gas under ambient conditions in the presence of triethylamine in THF-d(8) quantitatively yielded hydrido(amine) complex [Cp*Ir(H){kappa(2)(N,C)-NH2C(C6H5)(2)-2-C6H4}] (4). The C-N chelating Ir complex shows a higher catalytic activity than an N-N chelating complex, [Cp*Ir(NCCH3)(Tscydn)+SbF6- (3; Tscydn = N-(p-toluenesulfonyl)-1,2-cyclohexanediamime), that has been previously used for the asymmetric hydrogenation of acyclic imines. For example, the cationic Ir complex la promoted the hydrogenation of N-(1-phenylethylidene)benzylamine under 30 atm at 30 degrees C in the presence of excess AgSbF6 to produce the corresponding amine in 97% yield within 2 h. The cationic Rh complexes 2 serve as efficient catalysts for hydrogenative condensation of nitriles in the presence of AgSbF6, producing dibenzylamines selectively even at 60 degrees C.

  DOI：

  10.1021/acs.organomet.6b00133

文献信息

• Synthesis and Reactivities of Cp*Ir Amide and Hydride Complexes Bearing C−N Chelate Ligands
  作者：Sachiko Arita、Takashi Koike、Yoshihito Kayaki、Takao Ikariya

  DOI：10.1021/om800124f

  日期：2008.6.1

  A series of 16-electron Cp*Ir amide complexes with C-N chelating ligands, Cp*Ir[kappa(2)(NC)-(NHCR2-2-C6H4)] (2a: R = C6H5, 2b: R = CH3) and the chiral version, Cp*Ir[kappa(2)(N,C)-(R)-NHCH(CH3)-2-C10H6}] (2e), were obtained in good to excellent yields from reactions of 18-electron iridium amine complexes, Cp*IrCl[kappa(2)(N,C)-(NH2CR2-2-C6H4)] (1a: R = C6H5, 1b: R = CH3) and Cp*IrCl[kappa(2)(N,C)-(R)-NH2CH(CH3)-2-C10H6}] (le), with a base. The amido complexes 2 readily reacted with 2-propanol to convert into hydrido(amine) complexes 3 in almost quantitative yields. The chiral amido complex has proven to serve as an efficient catalyst for asymmetric transfer hydrogenation of acetophenone with 2-propanol, giving 1-phenylethanol with a moderate ee. The Bronsted basicity on the metal-NH moiety in the amido complexes was evaluated by deprotonation of acetic acid, dimethyl malonate, and acetone, leading to the corresponding acetato(amine) complex 4 and alkyl(amine) complexes 5 and 6, respectively, indicating that the amido-Ir complexes bearing the C-N chelate have more basic properties than those with N-sulfonylated diamine ligands.