trans-[Pd(2,4-dimethylpyridine)2Cl2] | 37991-40-5

• 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: trans-[Pd(2,4-dimethylpyridine)2Cl2]
• 英文别名: PdCl₂(2,4-Me₂Py)₂；PdCl2(2,4-Me2Py)2；Dichlorobis(2,4-dimethylpyridine)palladium；dichloropalladium;2,4-dimethylpyridine
• CAS: 37991-40-5
• 化学式: C₁₄H₁₈Cl₂N₂Pd
• 分子量: 391.636
• InChiKey: XBAAWIWIMABHMB-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  4.77
• 重原子数：
  19
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.29
• 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：

  2,4-二甲基吡啶 、 palladium dichloride 以 乙腈 为溶剂， 反应 24.0h， 生成 trans-[Pd(2,4-dimethylpyridine)2Cl2]
  参考文献：
  名称：

  Pd（II）配合物与吡啶作为催化剂用于CO / H 2 O还原芳香硝基化合物的应用

  摘要：

  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）。

  DOI：

  10.1021/acs.oprd.5b00273
• 作为试剂：
  描述：

  乙醇 、 一氧化碳 、 硝基苯 在 2,4-二甲基吡啶 、 trans-[Pd(2,4-dimethylpyridine)2Cl2] 、 碘 、 铁粉 作用下， 180.0 ℃ 、4.0 MPa 条件下， 反应 2.0h， 以36 mmol的产率得到N-二苯尿烷
  参考文献：
  名称：

  Catalytic activity of PdCl2 complexes with pyridines in nitrobenzene carbonylation

  摘要：

  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.

  DOI：

  10.1016/j.molcata.2011.01.007

文献信息

• Displacement of organic sulphides by amines in trans-dichlorobis(organic sulphide)palladium(II) complexes
  作者：Lucio Cattalini、Matteo Cusumano、Sandro Degetto

  DOI：10.1039/dt9780000012

  日期：——

  nucleophilic displacement of a variety of organic sulphides RSR′ from complexes of the type trans-[Pd(RSR′)2Cl2] by amines of different basicity and steric hindrance have been measured in 1,2-dimethoxyethane at 25 °C. The overall reaction occurs in two separate stages, the first being much faster than the second. The investigated processes correspond to the reaction: trans-[Pd(RSR′)2Cl2]+ amine →trans-

  在1,2-二甲氧基乙烷中，已测定了不同碱性和空间位阻胺从反式-[Pd（RSR'）2 Cl 2 ]类型络合物中各种有机硫化物RSR'的亲核取代动力学，已在25°C下进行了测量。 C。整个反应分两个阶段进行，第一个阶段比第二个阶段快得多。研究的过程与该反应相对应：反式-[Pd（RSR'）2 Cl 2 ] +胺→反式-[Pd（RSR'）（胺）-Cl 2] + RSR'（胺＝吡啶或取代的吡啶）。亲核取代遵守通常的二项速率方程。比较和讨论了反应速率，一种络合物对单个进入胺的区分，以及单个硫化物被给定胺置换后的不稳定性。
• Promoting antihepatocellular carcinoma activity against human HepG2 cells via pyridine substituted palladium complexes: in vitro evaluation and QSAR studies
  作者：ÖĞÜNÇ MERAL、FATİH MEHMET EMEN、EMİNE KUTLU、RUKEN ESRA DEMİRDÖĞEN、NESLİHAN KAYA KINAYTÜRK、GÖRKEM KISMALI、ŞEVKİNAZ DOĞAN

  DOI：10.55730/1300-0527.3536

  日期：——

  Bis(4-(4-nitrobenzyl)pyridine)dichloropalladium(II), [PdCl$_2}$L$^1}$$_2}$], bis(2-amino-5-bromopyridine)dichloropalladium(II), [PdCl$_2}$L$^2}$$_2}$], bis(2,4-dimethylpyridine)dichloropalladium(II), [PdCl$_2}$L$^3}$$_2}$], bis(3,4-dimethylpyridine)dichloropalladium(II), [PdCl$_2}$L$^4}$$_2}$] were prepared. The spectroscopic techniques (FT-IR and $^1}$H-NMR, $^13}$C-NMR) were used to characterize the compounds. Theoretical calculations were used to validate the experimental results. The LanL2DZ-based DFT/B3LYP method was used to define the most stable possible molecular structure for the complexes. Potential energy distribution analysis was performed to determine the theoretical vibration bands of the complexes. Molecular electrostatic potential maps, boundary molecular orbitals and Mulliken charge distribution were used to determine the active sites of the molecules. The interaction mechanisms between the complexes and liver cancer protein were investigated via molecular docking. The study on the antiproliferative effects of these complexes on hepatocellular carcinoma cells (HepG2) showed that they are potent candidates for use against this liver cancer cell line.

  双(4-(4-硝基苄基)吡啶)二氯化钯(II)，[PdCl$_2}$L$^1}$_2}$]，双(2-氨基-5-溴吡啶)二氯化钯(II)，[PdCl$_2}$L$^2}$_2}$]、制备了双(2,4-二甲基吡啶)二氯化钯(II)、[PdCl$_2}$L$^3}$_2}$]、双(3,4-二甲基吡啶)二氯化钯(II)、[PdCl$_2}$L$^4}$_2}$]。利用光谱技术（傅立叶变换红外光谱和 $^1}$H-NMR、$^13}$C-NMR）对化合物进行了表征。理论计算用于验证实验结果。使用基于 LanL2DZ 的 DFT/B3LYP 方法确定了复合物最稳定的分子结构。通过势能分布分析，确定了复合物的理论振动带。分子静电位图、边界分子轨道和 Mulliken 电荷分布被用来确定分子的活性位点。通过分子对接研究了复合物与肝癌蛋白之间的相互作用机制。关于这些复合物对肝癌细胞（HepG2）的抗增殖作用的研究表明，这些复合物对这种肝癌细胞系具有很强的抗癌作用。
• 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.
• 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.
• Coupling of Aryl Halides with Aryl Boronic Acids with P(C₆H₅)(2-C₆H₄Cl)₂ as the Supporting Ligand
  作者：Michelle R. Pramick、Sara M. Rosemeier、Maryann T. Beranek、Stephanie B. Nickse、Joshua J. Stone、Robert A. Stockland,、Steven M. Baldwin、Margaret E. Kastner

  DOI：10.1021/om020885i

  日期：2003.2.1

  The chlorinated triarylphosphine P(C6H5)(2-C6H4Cl)(2) (1) has been used as a supporting ligand in the Suzuki-Miyaura coupling of aryl boronic acids with aryl halides. Aryl bromides without ortho substituents were successfully coupled at room temperature, while reactions involving sterically hindered aryl bromides required slight heating (70 degreesC). Electron-deficient aryl chlorides were also successfully coupled with heating (90 degreesC). Key reaction parameters such as order of addition, choice of mineral base, solvent volume, temperature, 1/Pd ratio, as well as electronic and steric variation of the aryl halide have been investigated and are reported.