di-μ-chloro-bis{4-(N-2',6'-dimethyl­phenyl)­imino­me­thyl­[2.2]­­pa­racyclophan-5-yl-C,N}di­pal­ladi­um­(II) | 1190405-60-7

• 英文名称: di-μ-chloro-bis{4-(N-2',6'-dimethyl­phenyl)­imino­me­thyl­[2.2]­­pa­racyclophan-5-yl-C,N}di­pal­ladi­um­(II)
• 英文别名: (R_pl)-di-μ-chlorobis{5-[N(2',6'-dimethylphenyl)iminomethyl][2.2]paracyclophan-4-yl-C,N}dipalladium(II)
• CAS: 1190405-60-7；1190604-54-6；1190604-58-0
• 化学式: C₅₀H₄₈Cl₂N₂Pd₂
• 分子量: 960.691
• InChiKey: XLCXYODHWDGMEY-WGPUOOCUSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  di-μ-chloro-bis{4-(N-2',6'-dimethyl­phenyl)­imino­me­thyl­[2.2]­­pa­racyclophan-5-yl-C,N}di­pal­ladi­um­(II) 在 汞 作用下， 以 甲苯 为溶剂， 反应 48.0h， 以60%的产率得到rac-{4-(N-2,6-dimethylphenyl)iminomethyl[2.2]paracyclophane-5-yl-C,N}mercury(II) chloride
  参考文献：
  名称：

  Evidence on palladacycle-retaining pathway for Suzuki coupling. Inapplicability of Hg-drop test for palladacycle catalysed reactions

  摘要：

  Investigation of the model atroposelective Suzuki reaction catalysed by chiral CN-palladacycles have shown that two types of catalytic cycle may operate simultaneously, with strong dependence of their contributions upon the palladacycle structure and conditions used. Dominant contribution of palladacycle retaining pathway was provided by the non-metallocene planar chiral iminate CN-palladacycle (R-pl)-4a using as catalyst, in reaction performed in toluene under aerobic conditions with KF as a base, affording (S-a)-2-methoxy-1,1'-binaphthalene with enantioselectivity up to 53% ee. The catalyst was recovered almost quantitatively as an iodide-bridged dimer, whose structure was confirmed by an X-ray diffraction study of its phosphine derivative. It was also shown that the common Hg drop test was unsuitable for mechanistic testing of palladacycle-catalysed reactions because of the transmetallation product formation, whose structure was confirmed by an X-ray diffraction study. (C) 2013 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2013.03.050
• 作为试剂：
  描述：

  1-萘硼酸 、 1-碘-2-甲氧基萘 在 potassium fluoride 、 di-μ-chloro-bis{4-(N-2',6'-dimethyl­phenyl)­imino­me­thyl­[2.2]­­pa­racyclophan-5-yl-C,N}di­pal­ladi­um­(II) 作用下， 以 甲苯 为溶剂， 反应 168.0h， 以37.3%的产率得到
  参考文献：
  名称：

  Evidence on palladacycle-retaining pathway for Suzuki coupling. Inapplicability of Hg-drop test for palladacycle catalysed reactions

  摘要：

  Investigation of the model atroposelective Suzuki reaction catalysed by chiral CN-palladacycles have shown that two types of catalytic cycle may operate simultaneously, with strong dependence of their contributions upon the palladacycle structure and conditions used. Dominant contribution of palladacycle retaining pathway was provided by the non-metallocene planar chiral iminate CN-palladacycle (R-pl)-4a using as catalyst, in reaction performed in toluene under aerobic conditions with KF as a base, affording (S-a)-2-methoxy-1,1'-binaphthalene with enantioselectivity up to 53% ee. The catalyst was recovered almost quantitatively as an iodide-bridged dimer, whose structure was confirmed by an X-ray diffraction study of its phosphine derivative. It was also shown that the common Hg drop test was unsuitable for mechanistic testing of palladacycle-catalysed reactions because of the transmetallation product formation, whose structure was confirmed by an X-ray diffraction study. (C) 2013 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2013.03.050

文献信息

• When Applying the Mercury Poisoning Test to Palladacycle-Catalyzed Reactions, One Should Not Consider the Common Misconception of Mercury(0) Selectivity
  作者：Olga N. Gorunova、Ivan M. Novitskiy、Yuri K. Grishin、Igor P. Gloriozov、Vitaly A. Roznyatovsky、Victor N. Khrustalev、Konstantin A. Kochetkov、Valery V. Dunina

  DOI：10.1021/acs.organomet.8b00363

  日期：2018.9.10

  The aim of this study was to demonstrate the absolute necessity of control experiments for a correct interpretation of mercury drop test results when applied to mechanistic studies of palladacycle-catalyzed reactions. It was shown that the interaction of diverse azapalladacycles with metallic mercury leads to the formation of organomercuric chlorides during the redox-transmetalation process. The structure of these organomercurials was confirmed by elemental analysis, H-1, C-13H-1}, and Hg-199H-1} NMR spectra, X-ray diffraction analysis, and DFT calculations. The behavior and properties of C,N-mercuracycles bearing the weak and labile N center dot center dot center dot Hg bond are discussed on the basis of the temperature dependence of the NMR spectra and calculated thermodynamic parameters of the dechelation process.