2-(diethylaminomethyl)-6-(diphenylphosphinoxy)phenylchloropalladium(II) | 1000396-27-9

• 英文名称: 2-(diethylaminomethyl)-6-(diphenylphosphinoxy)phenylchloropalladium(II)
• CAS: 1000396-27-9
• 化学式: C₂₃H₂₅ClNOPPd
• 分子量: 504.304
• InChiKey: WOMXXLVTMURFIW-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 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：
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反应信息

• 作为产物：
  描述：

  Pd(COD)Cl₂ 、 在 potassium phosphate 作用下， 以 1,4-二氧六环 为溶剂， 反应 3.0h， 以35%的产率得到2-(diethylaminomethyl)-6-(diphenylphosphinoxy)phenylchloropalladium(II)
  参考文献：
  名称：

  Mechanistic Insights into Pincer-Ligated Palladium-Catalyzed Arylation of Azoles with Aryl Iodides: Evidence of a Pd^II–Pd^IV–Pd^II Pathway

  摘要：

  Pincer-based ((POCNR,2)-P-R2)PdCl complexes, along with CuI cocatalyst catalyze the arylation of azoles with aryl Iodides to give the 2-arylated azole products:Herein; we report an extensive mechanistic investigation for the direct arylation of azoles involving a well-defined and highly efficient ((POCNEt2)-P-iPr2)PdCl (2a) catalyst, which emphasizes a rare Pd-II-Pd-IV-Pd-II redox catalytic pathway. Kinetic studies and deuterium labeling experiments indicate that the C-H bond cleavage on azoles occurs via two distinct routes in, a reversible manner. Controlled reactivity of the catalyst 2a underlines the iodo derivative ((POCNEt2)-P-iPr2)PdI (3a) to be the resting state of the catalyst. The intermediate species ((POCNEt2)-P-iPr2)Pd-benzothiazolyl (4a) has been isolated and structurally, characterized. A determination of reaction rates of compound 4a with electronically different aryl iodides has revealed the kinetic significance of the oxidative addition of the C(sp(2))-X electrophile, aryl iodide, to complex 4a. Furthermore, the reactivity behavior of 4a suggests that the arylation of benzothiazole proceeds via an oxidative addition/reductive elimination pathway involving a ((POCNEt2)-P-iPr2)Pd-IV(benzothiazolyl)(Ar)I species, which is strongly supported by DFT calculations.

  DOI：

  10.1021/acs.organomet.6b00003

文献信息

• New PCN and PCP Pincer Palladium(II) Complexes:  Convenient Synthesis via Facile One-Pot Phosphorylation/Palladation Reaction and Structural Characterization
  作者：Jun-Fang Gong、Yan-Hui Zhang、Mao-Ping Song、Chen Xu

  DOI：10.1021/om7008364

  日期：2007.12.1

  A series of new PCN pincer palladium(II) complexes with phosphinito group 2a−d and 3 were conveniently prepared via facile one-pot phosphorylation/palladation reaction of pyrazolyl or amino-containing m-phenol derivatives with chlorophosphines and PdCl2. Two PCP pincer complexes 4a,b were also readily obtained from resorcinol in an analogous yet simplified manner. All of the new complexes have been

  与phosphinito组一系列新的PCN钳形钯（II）络合物2A - d和3分别经由吡唑基的容易一锅磷酸化/ palladation反应或方便地制备含氨基的米与chlorophosphines和的PdCl -苯酚衍生物2。从间苯二酚以类似但简化的方式也容易获得两种PCP钳夹复合物4a，b。所有这些新的配合物均已通过1 H NMR，13 C 1 H} NMR，31 P 11 H NMR，IR，ESI-MS和元素分析。另外，已经通过X射线单晶衍射确定了2a - d的分子结构。