cis-[Pd(tetrahydrothiophene)2(3,5-dichlorotrifluorophenyl)(C6F5)] | 202352-04-3

• 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: cis-[Pd(tetrahydrothiophene)2(3,5-dichlorotrifluorophenyl)(C6F5)]
• 英文别名: cis-[Pd(3,5-dichlorotrifluorophenyl)(pentafluorophenyl)(tetrahydrothiophene)2]；2,4-Dichloro-1,3,5-trifluorobenzene-6-ide;palladium(2+);1,2,3,4,5-pentafluorobenzene-6-ide;thiolane
• CAS: 202352-04-3
• 化学式: C₂₀H₁₆Cl₂F₈PdS₂
• 分子量: 649.792
• InChiKey: SOYXWBOZHWOMRY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.42
• 重原子数：
  33
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  50.6
• 氢给体数：
  0
• 氢受体数：
  12

反应信息

• 作为产物：
  描述：

  trans-[Pd(pentafluorophenyl)2(tetrahydrothiophene)2] 、 trans-[Pd(3,5-dichlorotrifluorophenyl)2(tetrahydrothiophene)2] 在 四氢噻吩 作用下， 以 氘代氯仿 为溶剂， 生成 cis-[Pd(tetrahydrothiophene)2(3,5-dichlorotrifluorophenyl)(C6F5)]
  参考文献：
  名称：

  An Aryl Exchange Reaction with Full Retention of Configuration of the Complexes:  Mechanism of the Aryl Exchange between [PdR₂L₂] Complexes in Chloroform (R = Pentahalophenyl, L = Thioether)

  摘要：

  The complexes [Pd(3,5-C6Cl2F3)(2)L-2] and [Pd(C6F5)(2)L-2] (L = SC4H8 (tht), or SMe2) react in CCl3D to give a mixture also containing the heteroaryl products [Pd(3,5-C6Cl2F3)(C6F5)L-2], whereas for L = PPh3, AsPh3, 2-picoline, 4-picoline, or 1/2COD, this exchange is not observed. The F-19 NMR kinetic study supports that the scrambling of the aryl groups takes place with retention of configuration at both Pd centers via a triply-bridged binuclear activated complex [L(C6Cl2F3)Pd(mu-C6Cl2F3)(mu-C6F5)(mu-L)Pd(C6F5)L].(double dagger) The aryl double bridge is supported by a bridging S-donor ligand facilitating an otherwise difficult exchange (not observed for other weak L ligands, such as picolines, lacking a second lone pair). This constitutes the first reported example of reversible migration of sigma-C-bonded groups between bis-organo Pd(II) complexes proceeding without cis-trans isomerization. The isomerization process is also observed, occurring at a much slower rate.

  DOI：

  10.1021/om970721f

文献信息

• An Aryl Exchange Reaction with Full Retention of Configuration of the Complexes:  Mechanism of the Aryl Exchange between [PdR₂L₂] Complexes in Chloroform (R = Pentahalophenyl, L = Thioether)
  作者：Arturo L. Casado、Juan A. Casares、Pablo Espinet

  DOI：10.1021/om970721f

  日期：1997.12.1

  The complexes [Pd(3,5-C6Cl2F3)(2)L-2] and [Pd(C6F5)(2)L-2] (L = SC4H8 (tht), or SMe2) react in CCl3D to give a mixture also containing the heteroaryl products [Pd(3,5-C6Cl2F3)(C6F5)L-2], whereas for L = PPh3, AsPh3, 2-picoline, 4-picoline, or 1/2COD, this exchange is not observed. The F-19 NMR kinetic study supports that the scrambling of the aryl groups takes place with retention of configuration at both Pd centers via a triply-bridged binuclear activated complex [L(C6Cl2F3)Pd(mu-C6Cl2F3)(mu-C6F5)(mu-L)Pd(C6F5)L].(double dagger) The aryl double bridge is supported by a bridging S-donor ligand facilitating an otherwise difficult exchange (not observed for other weak L ligands, such as picolines, lacking a second lone pair). This constitutes the first reported example of reversible migration of sigma-C-bonded groups between bis-organo Pd(II) complexes proceeding without cis-trans isomerization. The isomerization process is also observed, occurring at a much slower rate.