tris(pentafluorophenyl)osmium(IV)(SC6H4(SC6F5)-2) | 943305-57-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: tris(pentafluorophenyl)osmium(IV)(SC6H4(SC6F5)-2)
• 英文别名: [Os(SC6F5)3(SC6F4(SC6F5)-2)]；[Os(C6F5)3(SC6F4(SC6F5)-2)]
• CAS: 943305-57-5
• 化学式: C₃₀F₂₄OsS₅
• 分子量: 1166.82
• InChiKey: VJTWBHLLYSCOKD-UHFFFAOYSA-J

计算性质

• 辛醇/水分配系数(LogP)：
  11.86
• 重原子数：
  60.0
• 可旋转键数：
  7.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为产物：
  描述：

  四氧化锇 、 五氟苯硫酚 以 乙醇 为溶剂， 以18%的产率得到tris(pentafluorophenyl)osmium(IV)(SC6H4(SC6F5)-2)
  参考文献：
  名称：

  the（III）和O（IV）氟硫醇盐络合物的制备中的碳-氟键裂解。通过氟NMR赋值和通量过程测定氟。

  摘要：

  OsO4与HSR（R = C6F5，C6F4H-4，）在回流的乙醇中反应生成[Os（SC6F5）3（SC6F4（SC6F5）-2）]（1）和[Os（SC6F4H-4）3（SC6F3H-4） -（SC6F4H-4）-2）]（2），其中涉及CF键的断裂。在室温下，化合物[Os（SC6F5）3（PMe2Ph）2]或[Os（SC6F5）4（PMe2Ph）]与KOH（aq）在丙酮中反应，生成[Os（SC6F5）（SC6F4（SC6F4O- 2）-2）（PMe2Ph）2]（3），通过涉及两个CF键断裂的过程，而化合物[Os（SC6F4H）4（PPh3）]与丙酮中的KOH（aq）反应生成[Os （SC6F4H-4）2（SC6F3H-4-O-2）（PPh3）]（4），这也意味着CF键断裂。对1、2和4进行的单晶X射线衍射研究表明，这些化合物在基本为三角形-双锥体的几何结构中包括五配位的金属离子，而对顺磁性

  DOI：

  10.1021/ic0619660

文献信息

• Carbon−Fluorine Bond Activation in Thermolysis Reactions of the Osmium(IV) Perfluorothiolate Compounds [Os(SC₆F₅)₄(P(C₆H₄X-4)₃)] (X = CF₃, Cl, F, H, CH₃, and OCH₃)
  作者：Consuelo Mendoza、Sylvain Bernès、Hugo Torrens、Maribel Arroyo

  DOI：10.1021/om901065g

  日期：2010.6.28

  Thermolysis reactions of [Os(SC6F5)4(P(C6H4X-4)3)] (X = CF31, Cl 2, F 3, H 4, CH35, and OCH36) in refluxing toluene yield compounds [OsF(SC6F5)2(SC6F4(SC6F5)-2)(P(C6H4X-4)3)] (1a−6a) and [Os(SC6F5)2(SC6F4(SC6F5)-2)(C6H4X-4)] (1b−6b). In addition, [Os(SC6F5)3(SC6F4(SC6F5)-2)] (c) is yielded from 1−4 and 6, compounds [OsF(SC6F5)3(P(C6H4X-4)3)] [X = CF3 (1e), X = Cl (2e)] are also identified as products of the

  [OS（SC 6 F 5）4（P（C 6 H 4 X-4）3）]的热解反应（X = CF 3 1，Cl 2，F 3，H 4，CH 3 5和OCH 3 6）在甲苯中回流生成化合物[OSF（SC 6 F 5）2（SC 6 F 4（SC 6 F 5）-2）（P（C 6 H 4 X-4）3）]（1a - 6a）和[ OS（SC 6 F 5）2（SC 6 F 4（SC 6 F 5）-2）（C 6 H 4 X-4）]（1b - 6b）。此外，[ OS（SC 6 ˚F 5）3（SC 6 ˚F 4（SC 6 ˚F 5）-2）]（C ^）从得到1 - 4和6，化合物[OSF（SC 6 ˚F 5）3（P（C 6 H 4 X-4）3）] [X = CF 3（1e），X = Cl（2e）]也被确定为1和2的热分解反应的产物，而[OS（SC 6 ˚F 5）2（S 2 ç 6 ˚F 4）（P（C 6 H ^ 4 CH
• Five-coordinate pentafluorobenzothiolate osmium(IV) complexes [Os(SC6F5)4(P(C6H4X-4)3)] (X=OCH3, CH3, F, Cl or CF3): Solid and solution structural characterization
  作者：Maribel Arroyo、Consuelo Mendoza、Sylvain Bernès、Hugo Torrens、Hugo Morales-Rojas

  DOI：10.1016/j.poly.2009.05.044

  日期：2009.9

  The reactions of OSO4 with excess of HSC6F5 and P(CrH4X-4)(3) in ethanol afford the five-coordinate compounds [OS(SC6F5)(4)(P(C6H4X-4)(3))] where X = OCH3 1a and 1b, CH3 2a and 2b, F 3a and 3b, Cl 4a and 4b or CF3 Sa and 5b. Single crystal X-ray diffraction studies of 1 to 5 exhibit a common pattern with an osmium center in a trigonal-bipyramidal coordination arrangement. The axial positions are occupied by mutually trans thiolate and phosphane ligands, while the remaining three equatorial positions are occupied by three thiolate ligands. The three pentafluorophenyl rings of the equatorial ligands are directed upwards, away from the axial phosphane ligand in the arrangement "3-up" (isomers a). On the other hand P-31H-1} and F-19 NMR studies at room temperature reveal the presence of two isomers in solution: The "3-up" isomer (a) with the three C6F5-rings of the equatorial ligands directed towards the axial thiolate ligand, and the "2-up, 1-down" isomer (b) with two C6F5-rings of the equatorial ligands directed towards the axial thiolate and the C6F5-ring of the third. equatorial ligand directed towards the axial phosphane. Bidimensional F-19-F-19 NMR studies encompass the two sub-spectra for the isomers a ("3-up") and b ("2-up, 1-down"). Variable temperature F-19 NMR experiments showed that these isomers are fluxional. Thus, the F-19 NMR sub-spectra for the "2-up, 1-down" isomers (b) at room temperature indicate that the two S-C(F5 ligands in the 2-up equatorial positions have restricted rotation about their C-S bonds, but this rotation becomes free as the temperature increases. Room temperature F-19 NMR spectra of 3 and 5 also indicate restricted rotation around the Os-P bonds in the "2-up, 1-down" isomers (b). In addition, as the temperature increases, the F-19 NMR spectra tend to be consistent with an increased rate of the isomeric exchange. Variable temperature P-31(H-1) NMR studies also confirm that, as the temperature is increased, the a and b isomeric exchange becomes fast on the NMR time scale. (C) 2009 Elsevier Ltd. All rights reserved.