aqua[1,4-bis(3,5-ditrifluoromethylphenyl)-2,3-dimethyl-1,4-diaza-1,3-butadiene]methylpalladium(II) tetrafluoroborate | 609810-33-5

• 英文名称: aqua[1,4-bis(3,5-ditrifluoromethylphenyl)-2,3-dimethyl-1,4-diaza-1,3-butadiene]methylpalladium(II) tetrafluoroborate
• 英文别名: [((CF3)2ArDABMe)Pd(CH3)(H2O)][BF4]
• CAS: 609810-33-5
• 化学式: BF₄*C₂₁H₁₇F₁₂N₂OPd
• 分子量: 734.584
• InChiKey: NGSSBNLFOUSSGT-YUQRYZCMSA-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：

  aqua[1,4-bis(3,5-ditrifluoromethylphenyl)-2,3-dimethyl-1,4-diaza-1,3-butadiene]methylpalladium(II) tetrafluoroborate 在 benzene 作用下， 以 水 为溶剂， 生成 钯
  参考文献：
  名称：

  Arene C−H Bond Activation and Arene Oxidative Coupling by Cationic Palladium(II) Complexes

  摘要：

  N,N'-Diaryl-alpha-diimine-ligated Pd(II) dimethyl complexes ((tBu2Ar)DAB(Me))PdMe2 and {((CF3)2Ar)DAB(Me)} PdMe2 {(tBu2Ar)DAB(Me): ArN=C(CH3)-C(CH3)=NAr, Ar=3,5-di-tert-butylphenyl; ((CF3)2Ar) DAB(Me): Ar = 3,5-bis(trifluoromethyl)phenyl} undergo protonolysis with HBF4(aq) in trifluoroethanol (TFE) to form cationic complexes [(alpha-diimine)Pd(CH3)(H2O)][BF4]. The cations activate benzene C-H bonds at room temperature. Kinetic analyses reveal trends similar to those observed for the analogous platinum complexes: the C-H activation step is rate-determining (KIE = 4.1 +/- 0.5) and is inhibited by H2O. The kinetic data are consistent with a mechanism in which benzene substitution proceeds by a solvent-(TFE-) assisted associative pathway. Following benzene C-H activation under 1 atm O-2, the products of the reaction are biphenyl and a dimeric mu-hydroxide complex, [(alpha-diimine)Pd(OH)](2)[BF4](2). The Pd(0) formed in the reaction is reoxidized by O-2 to the dimeric mu-hydroxide complex after the oxidative C-C bond formation. The regioselectivity of arene coupling was investigated with toluene and alpha,alpha,alpha-trifluorotoluene as substrates.

  DOI：

  10.1021/om0303294
• 作为产物：
  描述：

  N,N’-bis-(3,5di(trifluoromethyl)phenyl)-2,3-dimethyl-1,4-diaza-1,3-butadiene 以 乙醚 、 水 为溶剂， 生成 aqua[1,4-bis(3,5-ditrifluoromethylphenyl)-2,3-dimethyl-1,4-diaza-1,3-butadiene]methylpalladium(II) tetrafluoroborate
  参考文献：
  名称：

  Arene C−H Bond Activation and Arene Oxidative Coupling by Cationic Palladium(II) Complexes

  摘要：

  N,N'-Diaryl-alpha-diimine-ligated Pd(II) dimethyl complexes ((tBu2Ar)DAB(Me))PdMe2 and {((CF3)2Ar)DAB(Me)} PdMe2 {(tBu2Ar)DAB(Me): ArN=C(CH3)-C(CH3)=NAr, Ar=3,5-di-tert-butylphenyl; ((CF3)2Ar) DAB(Me): Ar = 3,5-bis(trifluoromethyl)phenyl} undergo protonolysis with HBF4(aq) in trifluoroethanol (TFE) to form cationic complexes [(alpha-diimine)Pd(CH3)(H2O)][BF4]. The cations activate benzene C-H bonds at room temperature. Kinetic analyses reveal trends similar to those observed for the analogous platinum complexes: the C-H activation step is rate-determining (KIE = 4.1 +/- 0.5) and is inhibited by H2O. The kinetic data are consistent with a mechanism in which benzene substitution proceeds by a solvent-(TFE-) assisted associative pathway. Following benzene C-H activation under 1 atm O-2, the products of the reaction are biphenyl and a dimeric mu-hydroxide complex, [(alpha-diimine)Pd(OH)](2)[BF4](2). The Pd(0) formed in the reaction is reoxidized by O-2 to the dimeric mu-hydroxide complex after the oxidative C-C bond formation. The regioselectivity of arene coupling was investigated with toluene and alpha,alpha,alpha-trifluorotoluene as substrates.

  DOI：

  10.1021/om0303294