tetrakis(pentafluorobenzenethiolate)osmium(IV)(P(C6H4CH3-4)3) | 328564-88-1

• 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: tetrakis(pentafluorobenzenethiolate)osmium(IV)(P(C6H4CH3-4)3)
• CAS: 328564-88-1
• 化学式: C₄₅H₂₁F₂₀OsPS₄
• 分子量: 1291.07
• InChiKey: AOZMMGIAPYZCBN-UHFFFAOYSA-J

计算性质

• 辛醇/水分配系数(LogP)：
  13.52
• 重原子数：
  71.0
• 可旋转键数：
  12.0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  tetrakis(pentafluorobenzenethiolate)osmium(IV)(P(C6H4CH3-4)3) 以 甲苯 为溶剂， 以40%的产率得到[OsF(SC6F5)2(SC6F4(SC6F5)-2)(P(C6H4CH3-4)3)]
  参考文献：
  名称：

  IV（IV）全氟硫醇盐化合物[Os（SC 6 F 5）4（P（C 6 H 4 X-4）3）]的热解反应中的碳氟键活化（X = CF 3，Cl，F，H ，CH 3和OCH 3）

  摘要：

  [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

  DOI：

  10.1021/om901065g
• 作为产物：
  描述：

  四氧化锇 、 五氟苯硫酚 、 三对苯甲基膦 以 乙醇 为溶剂， 以50%的产率得到tetrakis(pentafluorobenzenethiolate)osmium(IV)(P(C6H4CH3-4)3)
  参考文献：
  名称：

  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

  摘要：

  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-31{H-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.

  DOI：

  10.1016/j.poly.2009.05.044