trans-[Pd(3,5-dichlorotrifluorophenyl)2(tetrahydrothiophene)2] | 202280-59-9

• 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: trans-[Pd(3,5-dichlorotrifluorophenyl)2(tetrahydrothiophene)2]
• 英文别名: trans-[Pd(tetrahydrothiophene)2(3,5-dichlorotrifluorophenyl)2]；trans-Pd(3,5-dichlorotrifluorophenyl)2(tetrahydrothiophene)2；2,4-Dichloro-1,3,5-trifluorobenzene-6-ide;palladium(2+);thiolane
• CAS: 202280-59-9；202352-03-2
• 化学式: C₂₀H₁₆Cl₄F₆PdS₂
• 分子量: 682.701
• InChiKey: BUQNNMWOCQNBRW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.45
• 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：
  10

反应信息

• 作为反应物：
  描述：

  trans-[Pd(3,5-dichlorotrifluorophenyl)2(tetrahydrothiophene)2] 、 三苯胂 以 二氯甲烷 为溶剂， 以99%的产率得到trans-[Pd(AsPh3)2(3,5-dichlorotrifluorophenyl)2]
  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
• 作为产物：
  描述：

  trans-[PdCl₂(THT)2] 、 3,5-dichloro-2,4,6-trifluorobenzenelithium 以 乙醚 为溶剂， 生成 trans-[Pd(3,5-dichlorotrifluorophenyl)2(tetrahydrothiophene)2] 、 trans-[Pd(3,5-dichlorotrifluorophenyl)2(tetrahydrothiophene)2]
  参考文献：
  名称：

  3,5-二氯三氟苯基配合物，具有简​​单19 F NMR结构探针的芳基衍生物。Pd和Pt配合物的一般前体的合成1

  摘要：

  高产率合成顺式-[MR 2（COD）]（M = Pd，Pt; R = 3,5-C 6 Cl 2 F 3），顺式-[MR 2（THF）2 ]（M = Pd; Pt），反式-[PdR 2 L 2 ]（L = tht; SMe 2），反式-[PtR 2（SMe 2）2 ]和[M 2（μ- Cl）2 R 2 L 2 ]（ M = Pd，L = NCPh，tht，SMe 2; 报告M = Pt，L = tht）。这些络合物是用于制备几乎以定量产率包含顺式-MR 2，反式-MR 2和MC1R部分的其他络合物的一般前体。因此，通过用其他配体置换COD，THF，tht或SMe 2，可以制备具有一个或两个芳基环的任何配合物的几乎任何异构体。与其他多氟苯基相比，这些配合物的19 F NMR光谱简单，并给出了这种部分氟化的配体的光谱优势的一些实例。

  DOI：

  10.1016/s0022-328x(97)00424-5

文献信息

• A Novel Reversible Aryl Exchange Involving Two Organometallics:  Mechanism of the Gold(I)-Catalyzed Isomerization of <i>trans</i>-[PdR₂L₂] Complexes (R = Aryl, L = SC₄H₈)
  作者：Arturo L. Casado、Pablo Espinet

  DOI：10.1021/om980283s

  日期：1998.8.1

  evidencing that the catalyzed isomerization takes place with aryl-group exchange between Pd(II) and Au(I). An associative mechanism passing through R-bridged intermediates [(tht)(R1)2Pd(μ-R2)Au(tht)] and a donor−acceptor activated complex [(tht)(R1)2(R2)Pd→Au(tht)]⧧ is proposed. The results suggest that the associative displacement of tht from 1a by the nucleophilic arylgold(I) complex to give [(tht)(R1)2Pd(μ-R2)Au(tht)]

  [AuR 1（THT）]（3a）（R 1 = 3,5-C 6 Cl 2 F 3，THT =四氢噻吩）非常有效地催化反式-[Pd（R 1）2（THT）2 ]的异构化1a）形成CDCl 3中的顺式-[Pd（R 1）2（THT）2 ] 。的19个F NMR动力学研究通向一级速率定律ř异= ķ异丙[ 1A ] =（ķ SPO +ķ猫[ 3A ]）[ 1A ]，其中ķ SPO =（1.50±0.03）×10 - 6个小号- 1和ķ猫=一个/（b + [THT]）与一个=（1.32±0.07）×10 - 4个小号- 1和b =（3.0±0.2）×10 - 5摩尔大号- 1（在304.4 K）。的反应1A和[AUR 2（THT）]（R 2 = C 6 ˚F 5）的产率顺式-[PdR 1 R 2（THT）2 ]和3a，证明催化的异构化发生在Pd（II）和Au（I）之间进行芳基交换。缔合机理穿过R-桥接中间体[（THT）（R