[PdCl(2,6-bis(di-tert-butylphosphinomethyl)pyridine)]Cl | 1206724-11-9

• 英文名称: [PdCl(2,6-bis(di-tert-butylphosphinomethyl)pyridine)]Cl
• CAS: 1206724-11-9
• 化学式: C₂₃H₄₃ClNP₂Pd*Cl
• 分子量: 572.875
• InChiKey: UTVDOGOSCMZENR-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 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：
  None
• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [PdCl(2,6-bis(di-tert-butylphosphinomethyl)pyridine)]Cl 在 KN(Si(CH₃)3)2 or (CH₃)3COK 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 生成 Li[PdMe(2,6-bis(di-tert-butylphosphinomethyl)pyridine(-2H))]
  参考文献：
  名称：

  Cationic, Neutral, and Anionic PNP Pd^II and Pt^II Complexes: Dearomatization by Deprotonation and Double-Deprotonation of Pincer Systems

  摘要：

  A series of cationic, neutral, and anionic Pd-II and Pt-II PNP (PNP = 2,6-bis-(di-tert-butylphosphinomethyl)pyridine) complexes were synthesized. The neutral, dearomatized complexes [(PNP*)MX] (PNP* = deprotonated PNP; M = Pd, Pt; X = Cl, Me) were prepared by deprotonation of the PNP methylene group of the corresponding cationic complexes [(PNP)MX][Cl] with 1 equiv of base (KN(SiMe3)(2) or (BuOK)-Bu-t), while the anionic complexes [(PNP**)MX]Y--(+) (PNP** = double-deprotonated PNP; Y = Li, K) were prepared by deprotonation of the two methylene groups of the corresponding cationic complexes with either 2 equiv of KN(SiMe3)(2) or an excess of MeLi. While the reaction of [(PNP)PtCl][Cl] with an excess of MeLi led only to the anionic complex without chloride substitution, reaction of [(PNP)PdCl][Cl] with an excess of MeLi led to the methylated anionic complex [(PNP**)PdMe]Li--(+). NMR studies, X-ray structures, and density functional theory (DFT) calculations reveal that the neutral complexes have a "broken" aromatic system with alternating single and double bonds, and the deprotonated arm is bound to the ring by an exocyclic C=C double bond. The anionic complexes are best described as a pi system comprising the ring carbons conjugated with the exocyclic double bonds of the deprotonated "arms". The neutral complexes are reversibly protonated to their cationic analogues by water or methanol. The thermodynamic parameters Delta H, Delta S, and Delta G for the reversible protonation of the neutral complexes by methanol were obtained.

  DOI：

  10.1021/ic902012z
• 作为产物：
  描述：

  2,6-双(二叔丁基膦基甲基)吡啶 、 trans-dichlorobis(dimethylsulfide)palladium(II) 以 二氯甲烷 为溶剂， 以99%的产率得到[PdCl(2,6-bis(di-tert-butylphosphinomethyl)pyridine)]Cl
  参考文献：
  名称：

  Cationic, Neutral, and Anionic PNP Pd^II and Pt^II Complexes: Dearomatization by Deprotonation and Double-Deprotonation of Pincer Systems

  摘要：

  A series of cationic, neutral, and anionic Pd-II and Pt-II PNP (PNP = 2,6-bis-(di-tert-butylphosphinomethyl)pyridine) complexes were synthesized. The neutral, dearomatized complexes [(PNP*)MX] (PNP* = deprotonated PNP; M = Pd, Pt; X = Cl, Me) were prepared by deprotonation of the PNP methylene group of the corresponding cationic complexes [(PNP)MX][Cl] with 1 equiv of base (KN(SiMe3)(2) or (BuOK)-Bu-t), while the anionic complexes [(PNP**)MX]Y--(+) (PNP** = double-deprotonated PNP; Y = Li, K) were prepared by deprotonation of the two methylene groups of the corresponding cationic complexes with either 2 equiv of KN(SiMe3)(2) or an excess of MeLi. While the reaction of [(PNP)PtCl][Cl] with an excess of MeLi led only to the anionic complex without chloride substitution, reaction of [(PNP)PdCl][Cl] with an excess of MeLi led to the methylated anionic complex [(PNP**)PdMe]Li--(+). NMR studies, X-ray structures, and density functional theory (DFT) calculations reveal that the neutral complexes have a "broken" aromatic system with alternating single and double bonds, and the deprotonated arm is bound to the ring by an exocyclic C=C double bond. The anionic complexes are best described as a pi system comprising the ring carbons conjugated with the exocyclic double bonds of the deprotonated "arms". The neutral complexes are reversibly protonated to their cationic analogues by water or methanol. The thermodynamic parameters Delta H, Delta S, and Delta G for the reversible protonation of the neutral complexes by methanol were obtained.

  DOI：

  10.1021/ic902012z