DPEPhosPd(Br)Me | 459868-21-4

• 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: DPEPhosPd(Br)Me
• 英文别名: bromo(Ph2PC6H4OC6H4PPh2)methylpalladium(II)；bromopalladium(1+);carbanide;[2-(2-diphenylphosphanylphenoxy)phenyl]-diphenylphosphane
• CAS: 459868-21-4
• 化学式: C₃₇H₃₁BrOP₂Pd
• 分子量: 739.924
• InChiKey: IOPZJHWWCNPGPO-UHFFFAOYSA-M

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：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  bromopalladium(1+);carbanide;(1Z,5Z)-cycloocta-1,5-diene 、 双(2-二苯基磷苯基)醚 以 苯 为溶剂， 生成 DPEPhosPd(Br)Me
  参考文献：
  名称：

  The coordination behaviour of large natural bite angle diphosphine ligands towards methyl and 4-cyanophenylpalladium(ii) complexes

  摘要：

  研究了中性和离子型4-氰基苯钯(II)和甲基钯(II)复合物的结构，这些复合物含有双齿磷配体，并在溶液和固态进行研究。采用了以喹啉和铁烯为主链的双膦配体。合成了新的双(烷基磷基)取代的Xantphos配体。通过¹H NMR和³¹P NMR光谱、导电性测量、紫外-可见光谱和X射线晶体学来阐明复合物的结构。磷配体的微小变化决定了配体的配位方式。观察到了各种双齿顺式和反式配位以及三齿P–O–P、P–S–P和P–Fe–P配位模式。

  DOI：

  10.1039/b111596k

文献信息

• Evidence for Single-Electron Pathways in the Reaction between Palladium(II) Dialkyl Complexes and Alkyl Bromides under Thermal and Photoinduced Conditions
  作者：Thomas L. Andersen、Søren Kramer、Jacob Overgaard、Troels Skrydstrup

  DOI：10.1021/acs.organomet.6b00893

  日期：2017.6.12

  Palladium(II) dialkyl complexes have previously been studied for their formation of alkanes through reductive elimination. More recently, these complexes, especially L2Pd-(CH2TMS)(2) derived from Pd(COD)(CH2TMS)(2), have found general use as palladium(0) precursors for stoichiometric formation of oxidative addition complexes through a two-electron reductive elimination/oxidative addition sequence. Herein, we report evidence for an alternative pathway, proceeding through single-electron elementary steps, when DPEPhosPd(CH2TMS)(2) is treated with an alpha-bromo-alpha,alpha-difluoroacetamide. This new pathway does not take place through a palladium(0) intermediate, neither does it afford the expected oxidative addition complexes. Instead, stoichiometric amounts of carbon-centered alkyl radicals are formed, which can be trapped in high yields either by TEMPO or by an arene, leading to alpha-aryl-alpha,alpha-difluoroacetamides. The same overall transformation takes place under both thermal conditions (70 degrees C) and irradiation with a household light bulb (at 30 degrees C). It is also demonstrated that DPEPhosPdMe(2), made in situ from Pd(TMEDA)Me-2, displays a similar initial reactivity. Finally, electronically and structurally different alkyl bromides were evaluated as reaction partners.