[Os(4,4'-dimethoxy-2,2'-bipyridyl)2Cl2] | 146863-76-5

• 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: [Os(4,4'-dimethoxy-2,2'-bipyridyl)2Cl2]
• 英文别名: Dichloroosmium;4-methoxy-2-(4-methoxypyridin-2-yl)pyridine
• CAS: 146863-76-5；128472-00-4
• 化学式: C₂₄H₂₄Cl₂N₄O₄Os
• 分子量: 693.585
• InChiKey: YNYVCJXIHOSCNP-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  5.7
• 重原子数：
  35
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  88.5
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  4-乙烯基吡啶 、 [Os(4,4'-dimethoxy-2,2'-bipyridyl)2Cl2] 在 sodium dithionite 作用下， 以 乙二醇 、 乙酸乙酯 为溶剂， 以75%的产率得到
  参考文献：
  名称：

  ‘Wiring’ of glucose oxidase and lactate oxidase within a hydrogel made with poly(vinyl pyridine) complexed with [Os(4,4′-dimethoxy-2,2′-bipyridine)₂Cl]^+/2+

  摘要：

  Glucose and lactate electrodes based on hydrogels made by crosslinking glucose oxidase and the redox polymer formed upon complexing poly(vinyl pyridine) (PVP) with [Os(dmo-bpy)(2)Cl](+/2+) (dmo-bpy = 4,4'-dimethoxy-2,2'-bipyridine) on vitreous carbon electrode surfaces have been investigated. The redox potential of the hydrogels was +35 mV vs. SCE and their glucose electrooxidation current reached a plateau at +150 mV vs. SCE. Urate and acetaminophen were not electrooxidized at this potential at rates that would interfere with the glucose and lactate assays. At a glucose concentration of 1 mM, the addition of 0.1 mM ascorbate increased the current by 17%. At 5 mM glucose, switching the atmosphere from argon to oxygen reduced the currents by 11%.

  DOI：

  10.1039/ft9969204131
• 作为产物：
  描述：

  diammonium hexachloroosmate(IV) 、 4,4'-二甲氧基-2,2'-联吡啶 在 sodium dithionite 作用下， 以 水 、 乙二醇 为溶剂， 以90%的产率得到[Os(4,4'-dimethoxy-2,2'-bipyridyl)2Cl2]
  参考文献：
  名称：

  ‘Wiring’ of glucose oxidase and lactate oxidase within a hydrogel made with poly(vinyl pyridine) complexed with [Os(4,4′-dimethoxy-2,2′-bipyridine)₂Cl]^+/2+

  摘要：

  Glucose and lactate electrodes based on hydrogels made by crosslinking glucose oxidase and the redox polymer formed upon complexing poly(vinyl pyridine) (PVP) with [Os(dmo-bpy)(2)Cl](+/2+) (dmo-bpy = 4,4'-dimethoxy-2,2'-bipyridine) on vitreous carbon electrode surfaces have been investigated. The redox potential of the hydrogels was +35 mV vs. SCE and their glucose electrooxidation current reached a plateau at +150 mV vs. SCE. Urate and acetaminophen were not electrooxidized at this potential at rates that would interfere with the glucose and lactate assays. At a glucose concentration of 1 mM, the addition of 0.1 mM ascorbate increased the current by 17%. At 5 mM glucose, switching the atmosphere from argon to oxygen reduced the currents by 11%.

  DOI：

  10.1039/ft9969204131

文献信息

• Dipyridophenazine Complexes of Os(II) as Red-Emitting DNA Probes:  Synthesis, Characterization, and Photophysical Properties
  作者：R. Erik Holmlin、Johanna A. Yao、Jacqueline K. Barton

  DOI：10.1021/ic9808955

  日期：1999.1.1

  Polypyridyl complexes of Os(II) bearing one dipyridophenazine (dppz) derivative and two ancillary ligands derived from bipyridine (bpy) or phenanthroline (phen) exhibit emission maxima at similar to 740 nm and average excited-state lifetimes in the 10 ns range upon binding to DNA by preferential intercalation of the dppz ligand. A family of [Os(L-1)(L-2)(L-3)](2+) and [Os(L-1)(2)(L-2)](2+) complexes with simple modifications in the ancillary phen or bpy ligands (L-1 and L-3) as well as the intercalating dppz ligand (L-2) was prepared. By cyclic voltammetry, electron-donating substituents on the ancillary ligands lowered the Os(3+/2+) reduction potential but did not affect the reduction potential of the dppz ligand. A methyl substituent at the 7-, 8-, or 6-position of the dppz ligand shifted the phenazine reduction toward the negative but did not affect the Os(3+/2+) potential. Absorption titrations indicated intercalative binding to DNA with high affinity (K-B similar to 10(6) M-1) for the family of complexes, although at high ratios (50:1) of base pairs to metal, complexes with ancillary 4,7-dimethylphenanthroline or 4,4'-dimethylbipyridine ligands exhibit less hypochromism (26-27%) in the pi-pi* transition on the dppz ligand compared to complexes with 5,6-dimethylphenanthroline (30-37%) or the parent phen (31-35%). By steady-state and time-resolved emission spectroscopy, complexes bound to DNA by intercalation with substituents on the 4,7- or 4,4'-positions of the ancillary phen or bpy displayed lower quantum yields for emission (Phi(em)) compared to complexes with the parent phen, while complexes with methyl substituents on the dppz ligand had the greatest Phi(em). Studies with poly d(AT), poly d(GC), and mixed-sequence DNA revealed that the emission yields are also sequence-dependent. Comparative luminescence studies in CH2Cl2 demonstrated that these effects arise from a combination of (i) the inherent sensitivity of the excited state to ligand structure and (ii) perturbations in DNA binding geometry introduced by substituents on the ancillary and intercalating ligands. Our results clarify the relationships between ligand architecture and emission yield and lifetime in the presence and absence of DNA and illustrate the utility of dppz complexes of Os(II) as luminescent probes for DNA.
• Effect of Electrode Density of States on the Heterogeneous Electron-Transfer Dynamics of Osmium-Containing Monolayers
  作者：Robert J. Forster、Paul Loughman、Tia E. Keyes

  DOI：10.1021/ja002616u

  日期：2000.12.1

  Dense monolayers of [Os(OMe-bpy)(2)(p3p)Cl](I+), where OMe-bpy is 4,4'-dimethoxy-2,2'-bipyridyl and p3p is 4,4'-trimethylenedipyridine, have been formed by spontaneous adsorption onto clean platinum, mercury, gold, silver, carbon, and copper microelectrodes. These systems have been used to probe the influence of the electrode density of states on the rate of electron transfer across the electrode/monolayer interface. Monolayers on each material exhibit well-defined voltammetry for the Os2+/3+ redox reaction where the supporting electrolyte is aqueous 1.0 M NaClO4. The high scan rate (> 2000 V s(-1)) voltammetric response has been modeled using a nonadiabatic electron-transfer model. The standard heterogeneous electron-transfer rate constant, k(o), depends on the identity of the electrode material, e.g., k(o) is 6 x 10(4) and 4 x 10(3) s(-1) for platinum and carbon electrodes, respectively. Chronoamperometry, conducted on a microsecond rime scale, has been used to probe the potential dependence of the heterogeneous electron-transfer rate constant. These values range from (4.0 +/- 0.2) x 10(4) to (3.0 +/- 0.3) x 10(3) s(-1) on going from platinum to carbon electrodes. Temperature-resolved chronoamperometry and cyclic voltammetry reveal that the electrochemical activation enthalpy, DeltaH(double dagger), and the reaction entropy, DeltaS(RC)(double dagger), are both independent of the electrode material having values of 11.1 +/- 0.5 kJ mol(-1) and 29.6 +/- 2.4 J mol(-1) K-1, respectively. The effect of electrode material on the preexponential factors is discussed in terms of the electrode density of states. These experimental data indicate that the heterogeneous electron-transfer rate for a nonadiabatic process is not simply proportional to the density of states but is modulated by the electronic coupling efficiency. Moreover, the matrix coupling elements, H-AB, are between 0.1 and 0.5 J mol(-1), which is approximately 4 orders of magnitude smaller than those found from studies of intervalence charge-transfer intensities within comparable dimeric complexes.
• ‘Wiring’ of glucose oxidase and lactate oxidase within a hydrogel made with poly(vinyl pyridine) complexed with [Os(4,4′-dimethoxy-2,2′-bipyridine)₂Cl]^+/2+
  作者：Gregg Kenausis、Chris Taylor、Ioanis Katakis、Adam Heller

  DOI：10.1039/ft9969204131

  日期：——

  Glucose and lactate electrodes based on hydrogels made by crosslinking glucose oxidase and the redox polymer formed upon complexing poly(vinyl pyridine) (PVP) with [Os(dmo-bpy)(2)Cl](+/2+) (dmo-bpy = 4,4'-dimethoxy-2,2'-bipyridine) on vitreous carbon electrode surfaces have been investigated. The redox potential of the hydrogels was +35 mV vs. SCE and their glucose electrooxidation current reached a plateau at +150 mV vs. SCE. Urate and acetaminophen were not electrooxidized at this potential at rates that would interfere with the glucose and lactate assays. At a glucose concentration of 1 mM, the addition of 0.1 mM ascorbate increased the current by 17%. At 5 mM glucose, switching the atmosphere from argon to oxygen reduced the currents by 11%.