[PdMe(2,6-bis(di-tert-butylphosphinomethyl)pyridine)]Cl | 1206724-13-1

• 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: [PdMe(2,6-bis(di-tert-butylphosphinomethyl)pyridine)]Cl
• CAS: 1206724-13-1
• 化学式: C₂₄H₄₆NP₂Pd*Cl
• 分子量: 552.456
• InChiKey: HPKJXERFSPJNDI-UHFFFAOYSA-M

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：

  [PdMe(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 为溶剂， 以67%的产率得到[Pd(1,2-bis[(di-tert-butylphosphino)methyl]pyridine(-1H))(CH3)]
  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：

  chloromethyl(1,5-cyclooctadiene)palladium(II) 、 2,6-双(二叔丁基膦基甲基)吡啶 以 二氯甲烷 为溶剂， 反应 2.0h， 以61%的产率得到[PdMe(2,6-bis(di-tert-butylphosphinomethyl)pyridine)]Cl
  参考文献：
  名称：

  存在分子氧的钳夹连接的PdII-Me复合物的光解作用

  摘要：

  The reactions of t-BuPNP and t-BuPCP Pd-II-Me complexes (t-BuPNP = 2,6-bis[(di-tert-butylphosphino)methyl]pyridine and t-BuPCP = 2,6-bis[(di-tert-butylphosphino)methyl]phenyl) with O-2 are described and compared with the reported O-2 reactivity of related Pd-II-Me complexes. [(t-BuPNP)PdMe] Cl was found to react with O-2 upon photolysis resulting in oxidation of the pincer ligand backbone to produce a (t-BuPNO)PdCl complex. In contrast, photolysis of (t-BuPCP)PdMe with O-2 resulted in oxidation of the Pd-Me group to form (t-BuPCP)PdOCO2H. Isotopic labeling, radical initiators, and solvent studies were used to gain insight into the mechanisms of these unusual reactions of late metal alkyls with molecular oxygen.

  DOI：

  10.1021/acs.organomet.7b00020