(2,6-bis(di-tert-butylphosphinomethyl)pyridine*)PdCl | 1202749-37-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: (2,6-bis(di-tert-butylphosphinomethyl)pyridine*)PdCl
• 英文别名: (PNP*)PdCl；[Pd(1,2-bis[(di-tert-butylphosphino)methyl]pyridine(-1H))Cl]；[PdCl(2,6-bis(di-tert-butylphosphinomethyl)pyridine(-H))]；ditert-butyl-[[(6Z)-6-(ditert-butylphosphanylmethylidene)pyridin-1-id-2-yl]methyl]phosphane;palladium(2+);chloride
• CAS: 1202749-37-8
• 化学式: C₂₃H₄₂ClNP₂Pd
• 分子量: 536.414
• InChiKey: HHCGBEATNDPFSX-KZYDBBBVSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  5.81
• 重原子数：
  28
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.74
• 拓扑面积：
  1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (2,6-bis(di-tert-butylphosphinomethyl)pyridine*)PdCl 在 氧气 作用下， 以 氘代苯 为溶剂， 以48%的产率得到6-(ditert-butylphosphanylmethyl)pyridine-2-carboxylate;palladium(2+);chloride
  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
• 作为产物：
  描述：

  [Pd(1,2-bis[(di-tert-butylphosphino)methyl]pyridine)Cl]BF4 在 NaN(SiMe₃)2 作用下， 以 四氢呋喃 为溶剂， 生成 (2,6-bis(di-tert-butylphosphinomethyl)pyridine*)PdCl
  参考文献：
  名称：

  阳离子Ag I（PNP tBu）物种充当PNP转移剂：Pd（PNP tBu）（烷基）配合物的简便合成及其与PCP tBu类似物的反应性

  摘要：

  描述了阳离子络合物1 [Ag（PNP tBu）] BF 4（PNP tBu = 1,2-双[（二叔丁基膦基甲基）甲基]吡啶的简单合成及其对金和钯的便捷的金属转移性能。通过X射线晶体学推论，相应的Au络合物[Au（PNP tBu）] 2（BF 4）2（2）以固态存在为二聚体。过渡金属化性质得到扩展，以包括Pd-烷基物质的形成。的反应1与0.5当量的Pd（烯丙基）（μ-Cl）的二聚体导致完全形成[钯（PNPTBU）（η 1 -烯丙基）] BF 4络合物3。还可以通过适当的Pd前体，通过这种跨金属化方法，以高收率制备类似的阳离子甲基（4），氰基苯基（5）和氯类（6）。对于配合物的分子结构3 - 5由X射线晶体学来建立。配合物4和6与NaN（SiMe 3）2的反应导致PNP主链去质子化和脱芳构化并形成中性Pd物种7和8，可以看作是经过深入研究的Pd（PCP tBu）复合物的二膦基-单酰胺基N-连接的类似物。这些中性的Pd（PN

  DOI：

  10.1021/om900862w

文献信息

• Synthesis and Characterization of Anionic, Neutral, and Cationic PNP Pincer Pd^IIand Pt^IIHydrides
  作者：Wilson D. Bailey、Werner Kaminsky、Richard A. Kemp、Karen I. Goldberg

  DOI：10.1021/om500054f

  日期：2014.5.27

  characterization of anionic, neutral, and cationic hydride complexes of platinum and palladium are reported utilizing the PNP (PNP = 2,6-bis(di-tert-butylphosphinomethyl)pyridine) ligand. Comparisons by IR spectroscopy and X-ray crystallography are made across the series. Evaluation of the metal hydride stretching frequencies of the cationic through anionic complexes shows a trend of increasing M–H

  报道了利用PNP（PNP ＝ 2，6-双（二叔丁基膦基甲基）吡啶）配体的铂和钯的阴离子，中性和阳离子氢化物配合物的合成和表征。在整个系列中通过IR光谱学和X射线晶体学进行了比较。对阳离子到阴离子配合物的金属氢化物拉伸频率的评估显示出M–H键活化增加的趋势。评估了这些金属氢化物与氧气的反应性，并将其与先前报道的氧气插入反应进行了比较。
• Cationic, Neutral, and Anionic PNP Pd^II and Pt^II Complexes: Dearomatization by Deprotonation and Double-Deprotonation of Pincer Systems
  作者：Moran Feller、Eyal Ben-Ari、Mark A. Iron、Yael Diskin-Posner、Gregory Leitus、Linda J. W. Shimon、Leonid Konstantinovski、David Milstein

  DOI：10.1021/ic902012z

  日期：2010.2.15

  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.