trans-[Pd(AsPh3)2(3,5-dichlorotrifluorophenyl)2] | 202280-80-6

• 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(AsPh3)2(3,5-dichlorotrifluorophenyl)2]
• 英文别名: trans-[Pd(3,5-C6Cl2F3)2(AsPh3)2]；cis-[Pd(3,5-dichloro-2,4,6-trifluorophenyl)2(AsPh3)2]；cis-Pd(AsPh3)2(3,5-dichloro-2,4,6-trifluorophenyl)2；cis-[Pd(3,5-C6Cl2F3)2(AsPh3)2]
• CAS: 202280-80-6；1046824-89-8
• 化学式: C₄₈H₃₀As₂Cl₄F₆Pd
• 分子量: 1118.83
• InChiKey: VXWHQXVAJHMYMI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  4-甲基吡啶 、 trans-[Pd(AsPh3)2(3,5-dichlorotrifluorophenyl)2] 以 二氯甲烷 为溶剂， 以99%的产率得到cis-[Pd(4-picoline)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-[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

文献信息

• Enthalpy of ligand substitution in cis organopalladium complexes with monodentate ligands
  作者：Gorka Salas、Juan A. Casares、Pablo Espinet

  DOI：10.1039/b910055e

  日期：——

  The enthalpy for the substitution reaction cis-[PdRf2(THF)2] + 2 L →cis-[PdRf2L2] + 2THF (THF = tetrahydrofuran) has been measured in THF by calorimetric methods for Rf = 3,5-dichloro-2,4,6-trifluorophenyl, L = PPh3, AsPh3, SbPh3, PMePh2, PCyPh2, PMe3, AsMePh2, or L2 = dppe (1,2-bis(diphenylphosphino)ethane), dppf (1,1′-bis(diphenylphosphino)ferrocene). The values determined show that the substitution enthalpy has a strong dependence on the electronic and steric properties of the ligand. The study of the consecutive substitution reactions cis-[PdRf2(THF)2] + L →cis-[PdRf2L(THF)] + THF, and cis-[PdRf2L(THF)] + L →cis-[PdRf2L2] + THF has been carried our for L = PPh3 and L = PCyPh2. The first substitution is clearly more favorable for the bulkier leaving ligand, but the second gives practically the same ΔH value for both cases, indicating that the differences in steric hindrance happen to compensate the electronic differences for both ligands. The X-ray structures of cis-[PdRf2(PMePh2)2], cis-[PdRf2(dppe)] and cis-[PdRf2(dppf)] are reported.

  通过量热方法在THF中测量了取代反应cis-[PdRf2(THF)2] + 2 L →cis-[PdRf2L2] + 2THF（THF = 四氢呋喃）的焓变，其中Rf = 3,5-二氯-2,4,6-三氟苯基，L = PPh3、AsPh3、SbPh3、PMePh2、PCyPh2、PMe3、AsMePh2或L2 = dppe（1,2-双(二苯膦)乙烷）、dppf（1,1'-双(二苯膦)二茂铁）。测定值表明，取代焓强烈依赖于配体的电子和立体性质。对连续取代反应cis-[PdRf2(THF)2] + L →cis-[PdRf2L(THF)] + THF和cis-[PdRf2L(THF)] + L →cis-[PdRf2L2] + THF的研究进行了L = PPh3和L = PCyPh2的情况。第一次取代显然对较大的离去配体更有利，但第二次取代实际上在两种情况下给出了相同的ΔH值，表明立体阻碍的差异恰好补偿了两种配体的电子差异。报道了cis-[PdRf2(PMePh2)2]、cis-[PdRf2(dppe)]和cis-[PdRf2(dppf)]的X射线结构。
• Strong Metallophilic Interactions in the Palladium Arylation by Gold Aryls
  作者：Mónica H. Pérez-Temprano、Juan A. Casares、Ángel R. de Lera、Rosana Álvarez、Pablo Espinet

  DOI：10.1002/anie.201108043

  日期：2012.5.14

  It's the second step that counts: Arylation of Pd by Au takes place through transition states and intermediates featuring strong Au⋅⋅⋅Pd metallophilic interactions (see picture). However, the aryl transfer from [AuArL] to [PdArClL2] is thermodynamically disfavored and will not occur unless an irreversible ArAr coupling from [PdAr2L2] follows.

  这是至关重要的第二步：Au通过过渡态和具有强Au·⋅·Pd亲金属相互作用的中间体进行Pd的钯化（见图）。然而，从[AuArL]芳转移到[PDArClL 2 ]在热力学上是不受欢迎，除非一个不可逆转的Ar不会发生氩从[PDAR联接2大号2 ]如下。
• Observation of a Hidden Intermediate in the Stille Reaction. Study of the Reversal of the Transmetalation Step
  作者：Mónica H. Pérez-Temprano、Ainara Nova、Juan A. Casares、Pablo Espinet

  DOI：10.1021/ja802994v

  日期：2008.8.13

  A study of the reaction of cis-[PdRf(2)(AsPh3)(2)] (Rf = 3,5-C6Cl2F3) with SnBu3 (that is the reversal of the natural Stille reaction of [PdRfl(AsPh3)(2)] with RfSnBu(3)) allows for the observation of cis-[PdRf(2)(AsPh3)(ISnBu3)], the expected intermediate from a cyclic transmetalation in the direct Stille reaction, thus providing experimental support to the operation of cyclic transmetalation pathways.