PdCl₂(2-ClPy)₂ | 1290633-18-9

• 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: PdCl₂(2-ClPy)₂
• 英文别名: PdCl2(2-ClPy)2；PdCl2(2-chloropyridine)2；Palladium, dichlorobis(3-chloropyridine-|EN)-, (SP-4-1)-；2-chloropyridine;dichloropalladium
• CAS: 1290633-18-9
• 化学式: C₁₀H₈Cl₄N₂Pd
• 分子量: 404.419
• InChiKey: HWLAQCOTBINWOP-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  4.85
• 重原子数：
  17
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  25.8
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  2-氯吡啶 、 palladium dichloride 以 乙腈 为溶剂， 生成 PdCl₂(2-ClPy)₂
  参考文献：
  名称：

  氯化钯与单取代吡啶的配合物的晶体结构，电子性质和细胞毒活性†

  摘要：

  钯（II）配合物由于其卓越的催化和生物活性而备受关注。在本研究中，对六个PdCl 2（XPy）2配合物（其中：Py =吡啶; 使用X = H，CH 3或Cl）来研究取代基对其晶体结构和电子性质的影响，并将结果与​​其催化和细胞毒性活性相结合。首次描述了复合物PdCl 2（3-MePy）2，PdCl 2（4-MePy）2和PdCl 2（2-ClPy）2的结构，并将我们的结果与整个系列的可用数据进行了比较六个复合体。所有化合物均显示出正方形的平面配位几何结构，其中钯离子配位了两个氮原子吡啶配体和两个氯原子处于反位。对于具有邻位取代的XPy配体的配合物，会发生取代基的顺式分布，而对于其他配体：3-MePy和3-ClPy –取代基处于反式位置。对于XPy，π–π *和n–π *跃迁的能量取决于XPy环中X取代基的位置和性质。形成复合物后，观察到π-π*的变色位移（24-34 nm）和n-π*谱带的红变色。PdCl

  DOI：

  10.1039/c1dt11412c

文献信息

• Application of Pd(II) Complexes with Pyridines as Catalysts for the Reduction of Aromatic Nitro Compounds by CO/H₂O
  作者：Agnieszka Krogul、Grzegorz Litwinienko

  DOI：10.1021/acs.oprd.5b00273

  日期：2015.12.18

  undertaken to minimize the cost of large-scale conversion of aromatic nitro compounds to amines. Toward this end, application of CO/H2O as a reducing agent instead of molecular hydrogen seems to be a promising method, and the process can be catalyzed by Pd(II) complexes. In this work, the catalytic activity of square planar complexes of general structure PdCl2(XnPy)2 (where XnPy = pyridine derivative) was

  为了使芳香族硝基化合物大规模转化为胺的成本最小化，已经进行了许多努力。为此，使用CO / H 2 O作为还原剂代替分子氢似乎是一种有前途的方法，并且该过程可以由Pd（II）配合物催化。在这项工作中，研究了具有一般结构PdCl 2（X n Py）2（其中X n Py =吡啶衍生物）的方形平面配合物的催化活性。尤其要注意X n Py（配体）的芳环和要还原的硝基化合物（YC 6 H 4 NO 2）中取代基的作用）。在YC 6 H 4 NO 2的芳香环中引入吸电子Y会提高转化率，这表明该过程的动力学类似于在不存在水的情况下用CO羰基合成硝基苯氮烯的过程（见J. Mol 。CATAL A：化学2011，337，9-16）。令人惊讶地，吸电子取代基掺入X n Py配体的芳环中也增加了YC 6 H 4 NO 2的转化率（与YC 6 H 4 NO 2底物的结构无关）。
• Tuning of the catalytic properties of PdCl2(XnPy)2 complexes by variation of the basicity of aromatic ligands
  作者：Agnieszka Krogul、Jadwiga Skupińska、Grzegorz Litwinienko

  DOI：10.1016/j.molcata.2014.01.020

  日期：2014.4

  The position and number of substituents in pyridine ligands (XnPy) were correlated with structural, physical, and chemical properties of PdCl2(XnPy)(2) complexes applied as catalysts for the carbonylation of aromatic nitrocompounds (phosgene-free method of carbamates production). Thermal stability and catalytic activity of PdCl2(XnPY)(2) complexes without steric hindrance increases with increasing XnPy's basicity whereas a decrease of thermal stability and catalytic activity of the complexes is observed for sterically crowded complexes (with the ortho-substituted XnPy). The complexes with X = Cl in meta- position of XnPy decompose to a mixture of PdCl2 and metallic Pd (similarly to complexes with MenPy) whereas complexes with ortho-chlorine (in XnPy) decompose to the organopalladium products. Therefore, two different mechanisms of thermal decomposition are proposed for PdCl2(ClnPy)(2) and PdCl2(MenPy)(2). The results of complex thermal and structural analysis of a series of PdCl2(XnPy)(2) complexes allow us to get insight into the mechanism of nitrobenzene (NB) carbonylation catalyzed by PdCl2(XnPY)(2) at 150-180 degrees C. We conclude that the electron transfer from Pd(0) to nitrobenzene is the rate determining step of catalytic cycle of NB carbonylation. (C) 2014 Elsevier B.V. All rights reserved.
• Catalytic activity of PdCl2 complexes with pyridines in nitrobenzene carbonylation
  作者：Agnieszka Krogul、Jadwiga Skupińska、Grzegorz Litwinienko

  DOI：10.1016/j.molcata.2011.01.007

  日期：2011.3

  Synthesis of square planar palladium(II) complexes of general structure PdCl2(XnPy)(2) (where: Py = pyridine; XnPy = 2-MePy: 3-MePy; 4-MePy; 2,4-Me2Py; 2,6-Me2Py; 2-CIPy; 3-CIPy and 3,5-Cl2Py) has been performed in order to study activity of these complexes as catalysts of nitrobenzene (NB) carbonylation - a process of industrial importance leading to production of ethyl N-phenylcarbamate (EPC). Electron withdrawing/electron donating properties of XnPy ligands (described by experimentally determined acidity parameter pK(a)) have been correlated with activities of PdCl2(X Py)2 complexes during NB carbonylation in presence of catalytic system PdCl2(XnPy)(2)/Fe/I-2/XnPy. We observed that conversions of substrates and yields of EPC increase within increasing basicity of XnPy ligand (for not sterically hindered XnPy's). On the basis of current work and our previous studies a detailed mechanism of catalytic carbonylation of NB is proposed. (C) 2011 Elsevier B.V. All rights reserved.
• One pot synthesis of ureas and carbamates via oxidative carbonylation of aniline-type substrates by CO/O2 mixture catalyzed by Pd-complexes
  作者：Agnieszka Krogul、Grzegorz Litwinienko

  DOI：10.1016/j.molcata.2015.06.027

  日期：2015.10

  Carbonylation of aromatic amines by direct insertion of carbon monoxide is catalyzed by PdCl2(XnPY)(2) complexes (where Py = pyridine, X=-CH3, -Cl; n=0-2) and gives, depending on the conditions, ethyl N-phenylcarbamates or N,N'-diphenylureas. For carbonylation of aniline, a proper choice of XnPy ligands in PdCl2(XnPY)(2)catalyst and application of molecular oxygen instead of nitrobenzene (conventionally used oxidant for carbonylations) allow to carry out the process under mild conditions with high yield and selectivity. The best results (75% yield of the main product with selectivity of catalyst above 90%) were obtained for the process catalyzed by PdCl2(XnPY)(2) complex at 100 degrees C and they were greatly improved in comparison to 41% yield and 68% selectivity obtained for CO/nitrobenzene used at 180 degrees C. (C) 2015 Elsevier B.V. All rights reserved.