{bis(2,2'-bipyridyl)(4,4'-bipyridyl)(chloro)osmium} hexafluorophosphate | 91190-06-6

• 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: {bis(2,2'-bipyridyl)(4,4'-bipyridyl)(chloro)osmium} hexafluorophosphate
• 英文别名: [osmium-bis(2,2'-bipyridyl)-4,4'-bipyridyl(Cl)]PF6；[Cl(2,2'-bipyridine)2Os(4,4'-bipyridine)]PF6
• CAS: 91190-06-6
• 化学式: C₃₀H₂₄ClN₆Os*F₆P
• 分子量: 839.178
• InChiKey: VHFMTEQFHJLYIC-UHFFFAOYSA-M

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：
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• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  {bis(2,2'-bipyridyl)(4,4'-bipyridyl)(chloro)osmium} hexafluorophosphate 、 lithium perchlorate 以 水 为溶剂， 以75%的产率得到[osmium-bis(2,2'-bipyridyl)-4,4'-bipyridyl(H2O)](ClO4)2
  参考文献：
  名称：

  四嗪桥锇二聚体：电化学与光诱导电子转移

  摘要：

  二聚体复合物的单分子层 [p0p Os(bpy)2 4-tet Os(bpy)2 Cl]3+，其中 p0p 是 4,4'-联吡啶，bpy 是 2,2'-联吡啶，4-tet 是 3 ,6-bis(4-pyridyl)-1,2,4,5-tetrazine 通过自发吸附在铂微电极上形成。这些单分子层是稳定的，并且两个金属中心都对 Os2+/3+ 氧化还原反应表现出明确的伏安响应。吸附等温线表明二聚体和模型单体的占据区域 [p0p Os(bpy)2 4-tet]2+ 相同，为 158 ± 14 A2。该结果与采用扩展配置而不是与电极表面共面的二聚体一致。高速计时电流法显示，“内部”[p0p Os(bpy)2 4-tet]2+ 和“外部”[4-tet Os(bpy)2Cl]+ 的标准异质电子转移速率常数 k部分是 (1.3 ± 0. 2) × 106 和 (1.1 ± 0.1) × 104 s-1，分别。重组能至少为

  DOI：

  10.1021/jp010948v
• 作为产物：
  描述：

  4,4'-联吡啶 、 ammonium hexafluorophosphate 、 锇二(2,2'-联吡啶)氯化物 以 甲醇 、 水 为溶剂， 生成 {bis(2,2'-bipyridyl)(4,4'-bipyridyl)(chloro)osmium} hexafluorophosphate
  参考文献：
  名称：

  Electrochemistry of Spontaneously Adsorbed Monolayers. Equilibrium Properties and Fundamental Electron Transfer Characteristics

  摘要：

  The effects of solvent, electrolyte, and temperature on the electrochemical response of spontaneously adsorbed monolayers of [Os(bpy)(2)Cl(pNp)](+), where bpy is 2,2'-bipyridyl and pNp is 4,4'-bipyridyl, 1,2-bis(4-pyridyl)ethane, or 4,4'-trimethylenedipyridine, are examined. In tetrahydrofuran oxidation of the redox centers causes association of an extra anion, while two extra anions are bound to the oxidized centers in aqueous media. In aqueous solutions containing hydrophilic anions, such as nitrate or chloride, little ion pairing is observed. The temperature dependence of the formal potential over the range -5 to 40 degrees C shows that the reaction entropy (Delta S(rc)degrees) is positive, indicating increased solvent ordering in the higher oxidation state. A linear correlation is observed between the experimental reaction entropies and those predicted by the Born dielectric continuum model in a range of solvents. A non-absorbing model compound, [Os(bpy)(2)(pyridine)Cl]PF6, typically exhibits considerably smaller Delta S(rc)degrees values, suggesting that the formation of a dense monolayer significantly affects the reaction entropy. The heterogeneous rate constant k for the Os2+/(3+) reaction has been evaluated using nanosecond time scale chronoamperometry. Importantly, k is approximately independent of the supporting electrolyte concentration over the range 0.1 to 1.0 M. This may suggest that ion pairing is an equilibrium reaction that either precedes or follows electron transfer. Tafel plots of the dependence of ln k on overpotential show curvature, indicating that the transfer coefficient is potential dependent. For sufficiently large overpotentials k tends to become independent of the free energy driving force, which is consistent with Marcus theory. The response is asymmetric with respect to overpotential, with the slope for the oxidation process tending toward zero more rapidly than that for the reduction process. This response can be modeled as a tunneling process between electronic manifolds on the two sides of the interface.

  DOI：

  10.1021/ja00091a057

文献信息

• Demadis, Konstantinos D.; Neyhart, Gregory A.; Kober, Edward M., Inorganic Chemistry, 1999, vol. 38, p. 5948 - 5959
  作者：Demadis, Konstantinos D.、Neyhart, Gregory A.、Kober, Edward M.、White, Peter S.、Meyer, Thomas J.

  DOI：——

  日期：——
• Goldsby, Kenneth A.; Meyer, Thomas J., Inorganic Chemistry, 1984, vol. 23, # 19, p. 3002 - 3010
  作者：Goldsby, Kenneth A.、Meyer, Thomas J.

  DOI：——

  日期：——