[Ir(η⁵ :κ¹-(2-[(2,3,4,5-tetramethylcyclopentadienyl)methyl]pyridine))Cl₂] | 378788-37-5

• 英文名称: [Ir(η⁵ :κ¹-(2-[(2,3,4,5-tetramethylcyclopentadienyl)methyl]pyridine))Cl₂]
• 英文别名: [Ir(η⁵ :κ¹-C₅Me₄CH₂py)Cl₂]；[(η5-(tetramethylcyclopentadienyl)methylpyridine)Ir(III)Cl2]
• CAS: 378788-37-5
• 化学式: C₁₅H₁₈Cl₂IrN
• 分子量: 475.441
• InChiKey: PQUJJUKUYBNUKK-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
  None
• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  水 、 [Ir(η⁵ :κ¹-(2-[(2,3,4,5-tetramethylcyclopentadienyl)methyl]pyridine))Cl₂] 、 silver tetrafluoroborate 以 水 为溶剂， 以98%的产率得到[(η5-(tetramethylcyclopentadienyl)methylpyridine)Ir(III)(H2O)2](BF4)2*H2O
  参考文献：
  名称：

  pH-Dependent Transfer Hydrogenation, Reductive Amination, and Dehalogenation of Water-Soluble Carbonyl Compounds and Alkyl Halides Promoted by Cp*Ir Complexes

  摘要：

  This paper reports pH-dependent transfer hydrogenation, reductive amination, and dehalogenation of water-soluble substrates with the organometallic aqua complexes [Cp*Ir-III(H2O)(3)](2+) (1, CP* = eta (5)-pentamethylcyclopentadienyl), [(Cp boolean AND py)Ir-III(H2O)(2)](2+) (2, Cp boolean AND py = eta (5-)(tetramethylcyclopentadienyl)methylpyridine), and [Cp*Ir-III(bpy)(H2O)(2+) (3, bpy = 2,2'-bipyridine) as catalyst precursors and the formate ions HCOONa and HCOONH4 as hydrogen donors. Because of the difference in the electron-donating ability of the Cp*, Cp boolean AND py, and bpy ligands, the Lewis acidity of the iridium ions of 1-3 are ordered in strength as follows: 1 > 2 > 3. Complexes 1-3 are reversibly deprotonated to form the catalytically inactive hydroxo complexes [(Cp*Ir-III)(2)(mu -OH)(3)(+) (5), [{(Cp boolean AND py)Ir-III}(2)(mu -OH)(2)](2+) (6), and [Cp*Ir-III(bpy)(OH)](+) (7) around pH 2.8, 4.5, and 6.6, respectively. The deprotonation behavior of 1-3 indicates that the more Lewis acidic iridium ions would lower the pK(a) values of the coordinated H2O ligands. As a function of pH, the catalyst precursors I and 3 react with the formate ions to form the hydride complexes [(Cp*Ir-III)(2)(mu -H)(mu -OH)(mu -HCOO)](+) (8) and [Cp*Ir-III(bpy)(H)](+) (9), respectively, which act as active catalysts in these catalytic reductions. A similar hydride complex would be formed from the reaction of 2 with the formate ions, though we have no definite structural information on the hydride complex. The structures of 3(OTf)(2).H2O (OTf = CF3SO3-), [(Cp boolean AND py)(IrCl2)-Cl-III] (4), 6(OTf)(2), 7(OTf). 2H(2)O, and S(PF6) were unequivocally determined by X-ray analysis.

  DOI：

  10.1021/om010523v
• 作为产物：
  描述：

  在 (methylpyridine)tetramethylcyclopentadiene 作用下， 以 乙醇 、 1,2-二氯乙烷 为溶剂， 以35%的产率得到[Ir(η⁵ :κ¹-(2-[(2,3,4,5-tetramethylcyclopentadienyl)methyl]pyridine))Cl₂]
  参考文献：
  名称：

  pH-Dependent Transfer Hydrogenation, Reductive Amination, and Dehalogenation of Water-Soluble Carbonyl Compounds and Alkyl Halides Promoted by Cp*Ir Complexes

  摘要：

  This paper reports pH-dependent transfer hydrogenation, reductive amination, and dehalogenation of water-soluble substrates with the organometallic aqua complexes [Cp*Ir-III(H2O)(3)](2+) (1, CP* = eta (5)-pentamethylcyclopentadienyl), [(Cp boolean AND py)Ir-III(H2O)(2)](2+) (2, Cp boolean AND py = eta (5-)(tetramethylcyclopentadienyl)methylpyridine), and [Cp*Ir-III(bpy)(H2O)(2+) (3, bpy = 2,2'-bipyridine) as catalyst precursors and the formate ions HCOONa and HCOONH4 as hydrogen donors. Because of the difference in the electron-donating ability of the Cp*, Cp boolean AND py, and bpy ligands, the Lewis acidity of the iridium ions of 1-3 are ordered in strength as follows: 1 > 2 > 3. Complexes 1-3 are reversibly deprotonated to form the catalytically inactive hydroxo complexes [(Cp*Ir-III)(2)(mu -OH)(3)(+) (5), [{(Cp boolean AND py)Ir-III}(2)(mu -OH)(2)](2+) (6), and [Cp*Ir-III(bpy)(OH)](+) (7) around pH 2.8, 4.5, and 6.6, respectively. The deprotonation behavior of 1-3 indicates that the more Lewis acidic iridium ions would lower the pK(a) values of the coordinated H2O ligands. As a function of pH, the catalyst precursors I and 3 react with the formate ions to form the hydride complexes [(Cp*Ir-III)(2)(mu -H)(mu -OH)(mu -HCOO)](+) (8) and [Cp*Ir-III(bpy)(H)](+) (9), respectively, which act as active catalysts in these catalytic reductions. A similar hydride complex would be formed from the reaction of 2 with the formate ions, though we have no definite structural information on the hydride complex. The structures of 3(OTf)(2).H2O (OTf = CF3SO3-), [(Cp boolean AND py)(IrCl2)-Cl-III] (4), 6(OTf)(2), 7(OTf). 2H(2)O, and S(PF6) were unequivocally determined by X-ray analysis.

  DOI：

  10.1021/om010523v

文献信息

• Structurally Strained Half-Sandwich Iridium(III) Complexes As Highly Potent Anticancer Agents
  作者：Ana C. Carrasco、Vanessa Rodríguez-Fanjul、Abraha Habtemariam、Ana M. Pizarro

  DOI：10.1021/acs.jmedchem.9b02000

  日期：2020.4.23

  )(C,N)]PF6, where C5Me4CH2py is 2-((2,3,4,5-tetramethylcyclopentadienyl)methyl)pyridine, and C,N is 2-phenylpyridine (1), 7,8-benzoquinoline (2), 1-phenylisoquinoline (3), 2-(p-tolyl)pyridine (4), 4-chloro-2-phenylquinoline (5), or 2-(2,4-difluorophenyl)pyridine (6), have been synthesized. The cyclopentadienyl ligand bears a tethered pyridine that binds to the metal center, resulting in an Ir(η5:κ1-C5Me4CH2pyN)

  六种式[Ir（η5：κ1-C5Me4CH2py）（C，N）] PF6的配合物，其中C5Me4CH2py为2-（（2,3,4,5-四甲基环戊二烯基）甲基）吡啶，C，N为2-苯基吡啶（1），7,8-苯并喹啉（2），1-苯基异喹啉（3），2-（对甲苯基）吡啶（4），4-氯-2-苯基喹啉（5）或2-（2,4 -二氟苯基）吡啶（6）已经合成。环戊二烯基配体带有与金属中心结合的束缚吡啶，形成Ir（η5：κ1-C5Me4CH2pyN）束缚环结构，这一点已通过X，1、2、4、5和6的晶体结构证实合成了1和2的非系链版本，以帮助结构和活性之间的明确关联。虽然非系链复合物对MCF7癌细胞（与顺铂相似）具有很高的效力，但带有系链环结构1-6的复合物却具有更高的效力（1-2个数量级）。另外，1-6破坏线粒体膜电位（ΔΨm）并诱导氧化应激。内部化研究与系链和非系链复合物中的细胞内积累和抗癌活性密切相关。我们提出了具
• Unambiguous Intracellular Localization and Quantification of a Potent Iridium Anticancer Compound by Correlative 3D Cryo X‐Ray Imaging
  作者：José Javier Conesa、Ana C. Carrasco、Vanessa Rodríguez‐Fanjul、Yang Yang、José L. Carrascosa、Peter Cloetens、Eva Pereiro、Ana M. Pizarro

  DOI：10.1002/anie.201911510

  日期：2020.1.13

  The iridium half-sandwich complex [Ir(η5 :κ1 -C5 Me4 CH2 py)(2-phenylpyridine)]PF6 is highly cytotoxic: 15-250× more potent than clinically used cisplatin in several cancer cell lines. We have developed a correlative 3D cryo X-ray imaging approach to specifically localize and quantify iridium within the whole hydrated cell at nanometer resolution. By means of cryo soft X-ray tomography (cryo-SXT),

  铱半三明治复合物[Ir（η5：κ1-C5Me4 CH2 py）（2-苯基吡啶）] PF6具有高度的细胞毒性：在几种癌细胞系中，其临床使用顺铂的效价高15-250倍。我们已经开发了一种相关的3D冷冻X射线成像方法，可以以纳米分辨率对整个水合细胞中的铱进行专门定位和量化。借助可在50 nm分辨率下提供细胞超微结构的超薄X射线断层扫描（cryo-SXT）和可在70 nm步长范围内提供元素灵敏度的超薄X射线荧光X线断层摄影术（cryo-XRF） ，我们已将铱抗癌剂专门定位于线粒体中。我们的方法可提供有关金属药物细胞内命运的独特信息，而无需化学固定，标记或机械操纵细胞。