cis-[Pd(SMe2)2(C6F5)2] | 202280-65-7

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 芳基卤化物
• 英文名称: cis-[Pd(SMe2)2(C6F5)2]
• CAS: 202280-65-7
• 化学式: C₁₆H₁₂F₁₀PdS₂
• 分子量: 564.807
• InChiKey: LTZJWFAWEQSCDK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 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：
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反应信息

• 作为反应物：
  描述：

  trans-[Pd(pentafluorophenyl)2(tetrahydrothiophene)2] 、 cis-[Pd(SMe2)2(C6F5)2] 以 氘代氯仿 为溶剂， 生成 cis-[Pd(tetrahydrothiophene)(SMe2)(C6F5)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

文献信息

• Intriguing Behavior of an Apparently Simple Coupling Promoter Ligand, PPh₂(<i>p</i>-C₆H₄–C₆F₅), in Their Pd Complexes
  作者：María Pérez-Iglesias、Rebeca Infante、Juan A. Casares、Pablo Espinet

  DOI：10.1021/acs.organomet.9b00460

  日期：2019.10.14

  in complex cis-[PdPf2Pd(LHF)2] (A) (Pf = C6F5). At 25 °C, complex A undergoes easy reductive elimination to decafluorobiphenyl and, competitively, isomerizes to trans-[Pd(C6F5)2Pd(LHF)2] via functionally three-coordinate intermediates cis-[PdPf2(LHF)(S)] with the fourth position empty or weakly protected (S= THF, OH2, or π-aryl). Unexpectedly, the direct reductive C6F5–C6F5 elimination is faster from

  配体PPh 2（p -C 6 H 4 –C 6 F 5）L HF是单齿联苯膦的一个例子，它允许两个膦与Pd顺式配位，就像在复杂的顺式-[PdPf 2 Pd（L HF）中）2 ]（A）（Pf ＝ C 6 F 5）。在25°C下，复合物A易于还原消除为十氟联苯，并且竞争地异构化为反式-[Pd（C 6 F 5）2 Pd（L HF）2 ]通过功能上三价的中间体顺式[PdPf 2（L HF）（S）]的第四位为空或弱保护（S = THF，OH 2或π-芳基）。出乎意料的是，从四坐标配合物A直接还原C 6 F 5 -C 6 F 5的速度要比仅具有一个强L HF的中间体更快。其原因是两个顺式L HF配体起着大咬合角和一些四面体变形的螯合物的作用。实际上，使用过量的L HF（Pd：L≪ 1：2），测得的Pf-Pf偶合势垒ΔG ‡ Pf-Pf = 23.1 kcal·mol –1，将其偶合和形成相应Pd 0催