[(C5Me5)ClIr(1,10-phenanthroline-5,6-dione)](PF6) | 670244-07-2

• 英文名称: [(C5Me5)ClIr(1,10-phenanthroline-5,6-dione)](PF6)
• CAS: 670244-07-2
• 化学式: C₂₂H₂₁ClIrN₂O₂*F₆P
• 分子量: 718.058
• InChiKey: UKSNPMQYMPHWJR-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
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• 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：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  bis[dichloro(pentamethylcyclopentadienyl)iridium(III)] 、 1,10-邻二氮杂菲-5,6-二酮 、 tert-butylammonium hexafluorophosphate(V) 以 丙酮 为溶剂， 以75%的产率得到[(C5Me5)ClIr(1,10-phenanthroline-5,6-dione)](PF6)
  参考文献：
  名称：

  Metal vs Ligand Reduction in Complexes of Dipyrido[3,2-a:2‘,3‘-c]phenazine and Related Ligands with [(C₅Me₅)ClM]⁺ (M = Rh or Ir):  Evidence for Potential Rather Than Orbital Control in the Reductive Cleavage of the Metal−Chloride Bond

  摘要：

  Complexes between the chlorometal(III) cations [(C5Me5)CIM](+), M = Rh or Ir, and the 1,10-phenanthroline-derived alpha-diimine (Nboolean ANDN) ligands dipyrido[3,2-a:2',3'-c]phenazine (dppz), 1,4,7,10-tetraazaphenanthrene (tap), or 1,10-phenanthroline-5,6-dione (pdo) were investigated by cyclic voltammetry, EPR, and UV-vis-NIR spectroelectrochemistry with respect to either ligand-based or metal-centered (and then chloride-dissociative) reduction. Two low-lying unoccupied molecular orbitals (MOs) are present in each of these three Nboolean ANDN ligands; however, their different energies and interface properties are responsible for different results. Metal-centered chloride-releasing reduction was observed for complexes of the DNA-intercalation ligands dppz and tap to yield compounds [(Nboolean ANDN)(C5Me5)M] in a two-electron step. The separation of alpha-diimine centered optical orbitals and phenazine-based redox orbitals is apparent from the EPR and UV-vis-NIR spectroelectrochemistry of [(dppz)(C5Me5)M](0/.-/2-). In contrast, the pdo complexes undergo a reversible one-electron reduction to yield o-semiquinone radical complexes [(pdo)(C5Me5)CIM](.) before releasing the chloride after the second electron uptake. The fact that the dppz complexes undergo a Cl--dissociative two-electron reduction despite the presence of a lowest lying pi* MO (b(1)(phz)) with very little overlap to the metal suggests that an unoccupied metal/chloride-based orbital is lower in energy. This assertion is confirmed both by the half-wave reduction potentials of the ligands (tap, -1.95 V; dppz, -1.60 V; pdo, -0.85 V) and by the typical reduction peak potentials of the complexes [(L)(C5Me5)CIM](PF6) (tap, -1.1 V; dppz, -1.3 V; pdo, -0.6 V; all values against Fc(+/0)).

  DOI：

  10.1021/ic0351388