1,1-dimethyl-3,3-methylenediimidazoline-2,2-diylidenepalladium(II) dichloride | 701301-55-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑啉类
• 英文名称: 1,1-dimethyl-3,3-methylenediimidazoline-2,2-diylidenepalladium(II) dichloride
• 英文别名: 1,1'-dimethyl-3,3'-methylene-4-diimidazolin-2,2'-diylidene palladium(II) dichloride；1,1'-bis(methyl)-3,3'-methylene-diimidazoline-2,2'-diylidene-palladium(II)-dichloride；(1,1'-dimethyl-3,3'-methylenediimidazolin-2,2'-diylidene)palladium(II) dichloride
• CAS: 701301-55-5
• 化学式: C₉H₁₂Cl₂N₄Pd
• 分子量: 353.547
• InChiKey: WXRJZKQMAFLXGK-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  1.75
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  13
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1,1-dimethyl-3,3-methylenediimidazoline-2,2-diylidenepalladium(II) dichloride 、 氯 以 N,N-二甲基甲酰胺 为溶剂， 以86%的产率得到
  参考文献：
  名称：

  双-N-杂环卡宾四氯化钯(IV)配合物：有机底物直接氯化和氧化的合成、反应性和机理

  摘要：

  本文介绍了通式 LPd(IV)Cl(4) [L = (NHC)CH(2) )(NHC)] 来自 LPd(II)Cl(2) 和 Cl(2)。在分子间、非螯合控制的转化中，LPd(IV)Cl(4) 与烯烃和炔烃反应生成 1,2-二氯化加合物。芳香族、苄基和脂肪族 CH 键转化为 C-Cl 键。对 18VE Pd(IV) 配合物进行了烯烃二氯化的详细机理研究。正溶剂效应以及探索环己烯和氯化物浓度对烯烃氯化速率影响的动力学测量支持第一步中的 Pd(IV)-Cl 电离。来自各种烯烃的产品立体化学和产品分布也支持 Cl(+)-从五配位 Pd(IV)-中间体 LPd(IV)Cl(3)(+) 转移到烯烃。1-己烯/3-己烯竞争实验排除了沿反应坐标形成 π-配合物以及还原消除过程中原位生成的 Cl(2)。相反，很可能发生配体介导的从 LPd(IV)Cl(3)(+) 到 π 系统的直接 Cl(+)-转移。类似地，CH

  DOI：

  10.1021/ja107342b
• 作为产物：
  描述：

  1,1'-dimethyl-3,3'-methylenediimidazolium bromide 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 生成 1,1-dimethyl-3,3-methylenediimidazoline-2,2-diylidenepalladium(II) dichloride
  参考文献：
  名称：

  Coordination polymers of silver(I) with bis(N-heterocyclic carbene): Structural characterization and carbene transfer

  摘要：

  Reactions of the ethylene- and methylene-bridged bis(imidazolium) salts with an equivalent amount of silver oxide in dichloromethane at room temperature produced readily the silver NHC compounds [Ag2LBr2]. These compounds are partially soluble in DMF. The X-ray structure determination on 3d (L = 1,1'-dibenzyl-3,3'-ethylenediimidazolin-2,2'-diylidene) reveals the formation of bromide bibridged (Ag2LBr2)(n) chains and a unique supramolecular motif with weak (AgAg)-Ag-..., interactions of 3.429 angstrom. Similar to monomeric silver(I) NHC complexes, the silver coordination polymers can also act as carbene transfer reagents for the formation of chelating palladium NHC complexes in excellent yields. (c) 2005 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2004.12.028

文献信息

• Syntheses and characterization of palladium(II) complexes with a bidentate bis-NHC ligand having methyl and aryl substituents on terminal nitrogen atoms
  作者：Takeyoshi Yagyu、Ayana Tsubouchi、Yuki Nishimura

  DOI：10.1016/j.jorganchem.2014.05.016

  日期：2014.9

  bromide was prepared as an intermediate for the syntheses of unsymmetrical bidentate bis-NHC ligands bearing methyl and aryl substituents on the terminal nitrogen atoms. Three bis-NHC ligand precursors and their corresponding palladium(II) complexes were also prepared. 1H NMR spectra of the imidazolium salts of the bidentate ligands implied that the carbene on a methyl-substituted imidazolylidene ring is

  咪唑鎓盐，Ñ -chloromethyl- Ñ '甲基咪唑溴化物制备作为中间体用于不对称双齿二NHC配位体轴承甲基和芳基取代基上的末端氮原子的合成。还制备了三种双-NHC配体前体及其相应的钯（II）配合物。双齿配体的咪唑鎓盐的1 H NMR光谱表明，甲基取代的咪唑基亚甲基环上的卡宾比芳基取代的环上的卡宾更强。钯（II）配合物的晶体结构显示扭曲的方形平面结构。该配合物在Heck反应中显示出良好的催化性能。
• Expedient Synthesis of Bis(imidazolium) Dichloride Salts and Bis(NHC) Complexes from Imidazoles Using DMSO as a Key Polar Additive
  作者：Kyle R. Penn、Evan J. Anders、Vincent N. G. Lindsay

  DOI：10.1021/acs.organomet.1c00592

  日期：2021.12.13

  A general approach for the synthesis of bis(imidazolium) dichloride salts from imidazoles and dichloroalkanes is reported. Typical limitations of this reaction for the formation of methylene-bridged derivatives are addressed herein through the use of excess CH2Cl2 in the presence of DMSO as a polar cosolvent, significantly improving the conversion rates presumably via stabilization of the initial SN2

  报道了从咪唑和二氯烷烃合成双（咪唑鎓）二氯化盐的一般方法。此处通过在DMSO 作为极性助溶剂存在下使用过量 CH 2 Cl 2来解决此反应对形成亚甲基桥接衍生物的典型限制，这可能是通过稳定初始 S N 2 转变显着提高转化率状态。该方法还被证明适用于从吡啶衍生物形成双（吡啶鎓）二氯化物盐，以及从咪唑直接合成金属-双（NHC）配合物。
• The counterion influence on the CH-activation of methane by palladium(II) biscarbene complexes – structures, reactivity and DFT calculations
  作者：Thomas Strassner、Michael Muehlhofer、Alexander Zeller、Eberhardt Herdtweck、Wolfgang A Herrmann

  DOI：10.1016/j.jorganchem.2004.02.013

  日期：2004.4

  results of the single-crystal X-ray structure determination of 1,1′-dimethyl-3,3′-methylene-4-diimidazolin-2,2′-diylidene palladium(II) bischloride (1) and 1,1′-dimethyl-3,3′-methylene-4-diimidazolin-2,2′-diylidene palladium (II) bis(trifluoro-acetate) 2 confirmed the structural similarity to the known corresponding palladium bromide and iodide complexes. Since free 1,1′-dimethyl-R-3,3′-methylene-4-diimidazolin-2

  新颖桥接钯（II）双卡宾络合物具有不同抗衡离子报道：1,1 ' -二甲基-3,3- ' -亚甲基-4- diimidazolin -2,2 ' -diylidene钯（II）bischloride（1）和双（三氟乙酸盐）（2）已经以高收率合成。两种络合物在甲烷催化转化为甲醇方面均具有活性，并显示出与以前发表的NHC催化剂相当的活性。单晶X-射线结构测定的1,1的结果“ -二甲基-3,3 ' -亚甲基-4- diimidazolin -2,2 ' -diylidene钯（II）bischloride（1）和1,1 ' -二甲基-3,3 '亚甲基-4- diimidazolin -2,2 ' -diylidene钯（II）二（三氟乙酸盐）2确认的结构相似的已知对应钯溴化物和碘化物络合物。由于游离1,1 ' -二甲基- [R -3,3 ' -亚甲基-4- diimidazolin -2,2 '
• Extension of the Alkane Bridge in BisNHC−Palladium−Chloride Complexes. Synthesis, Structure, and Catalytic Activity
  作者：Sebastian Ahrens、Alexander Zeller、Maria Taige、Thomas Strassner

  DOI：10.1021/om060577a

  日期：2006.10.1

  A series of bisNHC chelate ligands with alkyl bridges of different chain lengths and their palladium complexes have been prepared. The influence of the different bridges on the solid-state structure and reactivity of the complexes has been studied. The catalytic activity of the palladium complexes was successfully tested in the Mizoroki-Heck reaction and the catalytic CH activation of methane. The ethylene-bridged palladium complex showed the highest catalytic activity in the CH activation of methane and the Mizoroki-Heck coupling of bromoarenes, while for unreactive chloroarenes bisNHC complexes with longer bridges give better results.