(1,2,3,4,5-pentamethylcyclopentadienyl)IrCl[κ2(N,C)-{NHC(CH3)2-2-C6H4}] | 1033052-14-0

• 英文名称: (1,2,3,4,5-pentamethylcyclopentadienyl)IrCl[κ2(N,C)-{NHC(CH3)2-2-C6H4}]
• 英文别名: (1,2,3,4,5-pentamethylcyclopentadienyl)IrCl[κ²(N,C)-{NHC(CH₃)₂-2-C₆H₄}]；Cp*IrCl[κ²(N,C)-{NHC(CH₃)₂-2-C₆H₄}]；Cp*IrCl[κ₂(N,C)-{NH₂C(CH₃)₂-2-C₆H₄}]
• CAS: 1033052-14-0
• 化学式: C₁₉H₂₇ClIrN
• 分子量: 497.103
• InChiKey: BVPTYPUTTSLOGX-UHFFFAOYSA-M

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：

  (1,2,3,4,5-pentamethylcyclopentadienyl)IrCl[κ2(N,C)-{NHC(CH3)2-2-C6H4}] 在 t-BuOK 作用下， 以 二氯甲烷 为溶剂， 以88%的产率得到(1,2,3,4,5-pentamethylcyclopentadienyl)Ir-[κ²(N,C)-(NHC(CH₃₎₂-2-C₆H₄)]
  参考文献：
  名称：

  Synthesis and Reactivities of Cp*Ir Amide and Hydride Complexes Bearing C−N Chelate Ligands

  摘要：

  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.

  DOI：

  10.1021/om800124f
• 作为产物：
  描述：

  bis[dichloro(pentamethylcyclopentadienyl)iridium(III)] 、 Alpha,Alpha-二甲基苄胺 在 sodium acetate 作用下， 以 二氯甲烷 为溶剂， 以79%的产率得到(1,2,3,4,5-pentamethylcyclopentadienyl)IrCl[κ2(N,C)-{NHC(CH3)2-2-C6H4}]
  参考文献：
  名称：

  Synthesis and Reactivities of Cp*Ir Amide and Hydride Complexes Bearing C−N Chelate Ligands

  摘要：

  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.

  DOI：

  10.1021/om800124f
• 作为试剂：
  描述：

  八氟甲苯 在 (1,2,3,4,5-pentamethylcyclopentadienyl)IrCl[κ2(N,C)-{NHC(CH3)2-2-C6H4}] 、 potassium formate 作用下， 以 乙二醇二甲醚 、 水 为溶剂， 反应 2.0h， 以97%的产率得到2,3,5,6-四氟三氟甲苯
  参考文献：
  名称：

  使用具有双功能铱/ NH基团的氢转移催化剂对氟代芳烃进行加氢脱氟

  摘要：

  描述了使用2-丙醇或甲酸钾用转移氢化催化剂对氟代芳烃进行加氢脱氟。借助金属/ NH配合，衍生自苄基胺的C–N螯合Ir配合物即使在不存在氢硅烷或H 2气体的情况下，也可在环境条件下有效地促进涉及C–F键断裂的还原反应，从而导致部分氟化产品，收率高且选择性高。

  DOI：

  10.1021/acscatal.6b01590

文献信息

• Heterolysis of NH-Indoles by Bifunctional Amido Complexes and Applications to Carboxylation with Carbon Dioxide
  作者：Atsushi Ueno、Yoshihito Kayaki、Takao Ikariya

  DOI：10.1021/om500695a

  日期：2014.9.8
• Cationic Iridium and Rhodium Complexes with C–N Chelating Primary Benzylic Amine Ligands as Potent Catalysts for Hydrogenation of Unsaturated Carbon–Nitrogen Bonds
  作者：Yasuhiro Sato、Yoshihito Kayaki、Takao Ikariya

  DOI：10.1021/acs.organomet.6b00133

  日期：2016.5.9

  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.