[Ir(triflato)(CH3)(C5H4NC5H2NPh)(4,4'-di-tert-butyldipyridyl)] | 937206-05-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: [Ir(triflato)(CH3)(C5H4NC5H2NPh)(4,4'-di-tert-butyldipyridyl)]
• 英文别名: [Ir(OTf)(CH3)(C5H4NC5H2NPh)(4,4'-di-tert-butyl-2,2'-bipyridine)]；4-tert-butyl-2-(4-tert-butylpyridin-2-yl)pyridine;carbanide;iridium(3+);6-phenyl-2-pyridin-2-yl-3H-pyridin-3-ide;trifluoromethanesulfonate
• CAS: 937206-05-8
• 化学式: C₃₆H₃₈F₃IrN₄O₃S
• 分子量: 856.004
• InChiKey: YWVJSIDZSCGNJN-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  8.85
• 重原子数：
  48
• 可旋转键数：
  5
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  117
• 氢给体数：
  0
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  [Ir(triflato)(CH3)(C5H4NC5H2NPh)(4,4'-di-tert-butyldipyridyl)] 在 Hunig's base 作用下， 以 溶剂黄146 、 苯 为溶剂， 生成 [Ir(pyridine)(C6H5)(C5H4NC5H2NPh)(4,4'-di-tert-butyldipyridyl)](triflate)
  参考文献：
  名称：

  Cyclometalation of 6-Phenyl-2,2′-Bipyridine and Iridium: Synthesis, Characterization, and Reactivity Studies

  摘要：

  Heating the potential tridentate 6-(4-R-phenyl)-2,2'-bipyridine ligand la (R = H), and derivatives 1b (R = CMe3) and 1c (R = OH), with IrCl3 hydrate in 2-methoxyethanol or acetone/H2O gave the unexpected bidentate cyclometalated NC dinuclear complexes [Ir(NC)Cl-2(C5H5N)](2) (2a-cPy), as the major product. Altering the ligand/metal ratio from 1:1 to 2:1 produced a mixture of bis-cyclometalated complexes, Ir(NNC)(NC)Cl (3a,b), with tridentate and bidentate binding modes. Using discrete Ir-I synthons, such as Ir(dmso)(3)Cl or [Ir(cyclooctene)(2)Cl](2), gave a complicated mixture of products. However, when [Ir(C2H4)(2)Cl](2) was used, then the desired tridentate cyclometalated Ir(NNC) complex Ir(NNC)Et(CH4)Cl (4) was synthesized cleanly. The dinuclear complex 2a-Py was converted to the corresponding mononuclear dichloride complexes Ir(NC)(NN)Cl-2 (5a) upon refluxing with 4,4'-di-tert-butylbipyridine in N,N-dimethylacetamide (DMA). Treatment of 5a with ZnMe2 gives Ir(NC)(NNtBu)MeCl (6a). Abstraction of the chloride with AgOTF yields Ir(NC)(NNtBu)MeOTf (7a). Complex 7a undergoes stoichiometric CH activation with arenes and shows catalytic activity for the H/D exchange between benzene and ( trifluoro)acetic acids.

  DOI：

  10.1021/om900014h
• 作为产物：
  描述：

  [IrCl(CH₃)(C₅H₄NC₅H₂NPh)(4,4'-di-tert-butyldipyridyl)]*0.25C₆H₆ 、 silver trifluoromethanesulfonate 以 二氯甲烷 为溶剂， 以82.8%的产率得到[Ir(triflato)(CH3)(C5H4NC5H2NPh)(4,4'-di-tert-butyldipyridyl)]
  参考文献：
  名称：

  Cyclometalation of 6-Phenyl-2,2′-Bipyridine and Iridium: Synthesis, Characterization, and Reactivity Studies

  摘要：

  Heating the potential tridentate 6-(4-R-phenyl)-2,2'-bipyridine ligand la (R = H), and derivatives 1b (R = CMe3) and 1c (R = OH), with IrCl3 hydrate in 2-methoxyethanol or acetone/H2O gave the unexpected bidentate cyclometalated NC dinuclear complexes [Ir(NC)Cl-2(C5H5N)](2) (2a-cPy), as the major product. Altering the ligand/metal ratio from 1:1 to 2:1 produced a mixture of bis-cyclometalated complexes, Ir(NNC)(NC)Cl (3a,b), with tridentate and bidentate binding modes. Using discrete Ir-I synthons, such as Ir(dmso)(3)Cl or [Ir(cyclooctene)(2)Cl](2), gave a complicated mixture of products. However, when [Ir(C2H4)(2)Cl](2) was used, then the desired tridentate cyclometalated Ir(NNC) complex Ir(NNC)Et(CH4)Cl (4) was synthesized cleanly. The dinuclear complex 2a-Py was converted to the corresponding mononuclear dichloride complexes Ir(NC)(NN)Cl-2 (5a) upon refluxing with 4,4'-di-tert-butylbipyridine in N,N-dimethylacetamide (DMA). Treatment of 5a with ZnMe2 gives Ir(NC)(NNtBu)MeCl (6a). Abstraction of the chloride with AgOTF yields Ir(NC)(NNtBu)MeOTf (7a). Complex 7a undergoes stoichiometric CH activation with arenes and shows catalytic activity for the H/D exchange between benzene and ( trifluoro)acetic acids.

  DOI：

  10.1021/om900014h

文献信息

• Stoichiometric Oxy Functionalization and CH Activation Studies of Cyclometalated Iridium(III) 6-Phenyl-2,2‘-Bipyridine Hydrocarbyl Complexes
  作者：Kenneth J. H. Young、Oleg A. Mironov、Roy A. Periana

  DOI：10.1021/om0611002

  日期：2007.4.1

  A well-defined, thermal-, air-, and protic-stable, bis-bidentate, cyclometalated Ir(III) complex, Ir(NC)(NNtBu)CH3OTf, (2-CH3; NC = kappa(2)-6-phenyl-2,2'-bipyridine, NNtBu = kappa(2)-4,4'-di-tert-butyl-2,2'-bipyridine) has been shown to undergo oxy functionalization with oxidants such as PhI(X)(2) (X = OAc, TFA) to generate CH3X (X = OAc, TFA, OTf) in yields ranging from 36 to 67% in CH2Cl2 at ambient temperatures. 2-CH3 is also competent for CH activation, undergoing stoichiometric CH activation in benzene, and catalyzes the H/D exchange reaction between benzene and acids (acetic and trifluoroacetic acid).