trans-[platinum(II) dichloride bis(4-picoline)] | 72151-35-0

• 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-[platinum(II) dichloride bis(4-picoline)]
• 英文别名: trans-dichlorobis(4-methylpyridine)platinum(II)；trans-[PtCl2(4-methylpyridine)2]；trans-PtCl2(4-methylpyridine)2；trans-[Pt(4-picoline)2Cl2]；trans-[PtCl2(pic)2]；trans-[Pt^II(4-methylpyridine)₂Cl₂]；4-Methylpyridine;platinum(2+);dichloride
• CAS: 72151-35-0
• 化学式: C₁₂H₁₄Cl₂N₂Pt
• 分子量: 452.243
• InChiKey: QSELGNNRTDVSCR-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  4.16
• 重原子数：
  17
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  25.8
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  potassium cyanide 、 trans-[platinum(II) dichloride bis(4-picoline)] 以 甲醇 、 水 为溶剂， 生成 {Pt(4-methylpyridine)(CN)3}(1-)
  参考文献：
  名称：

  The cis- and trans-effects of cyanide in substitution at platinum(II)

  摘要：

  The cis- and trans-[Pt(am)2Cl2] isomers (am = dimethylamine, pyridine, 4-cyanopyridine, 4-chloropyridine, 2-methylpyridine, 4-methylpyridine, 2,4-dimethylpyridine, 4-ethylpyridine, morpholine or piperidine), react rapidly with excess CN- in methanol to form the corresponding cis- and trans-[Pt(am)2(CN)2] species which then react further to give [Pt(CN)4]2-. The kinetics of the slow step, [Pt(am)2(CN)2] + CN- --> [Pt(am)(CN)3]- + am, has been studied. In spite of the strong trans effect of CN- the trans species are all more reactive than the corresponding cis isomers. The second-order rate constants are sensitive to the nature of am; plots of log k2 against the pK(a) of Ham+ are linear but the slope for the trans isomers (-0.27) is much greater than that for the cis isomers (-0.07). The rate constants for the displacement of o-methyl substituted pyridines are smaller than predicted from their basicity. This steric hindrance effect is much more marked in the trans isomers. The complexes with am = NH3 and NH2Me are similarly less reactive than might be predicted but the effect is the same in both isomers. The results are explained in terms of the trans effect of cyanide and its effect upon the intrinsic reactivities and nucleophilic discriminations of the substrates.

  DOI：

  10.1039/dt9930000233
• 作为产物：
  描述：

  tetra(γ-picoline) platinum(II) Cl2 以 neat (no solvent) 为溶剂， 生成 trans-[platinum(II) dichloride bis(4-picoline)]
  参考文献：
  名称：

  Trans platinum(II) complexes with pyridine and substituted pyridines

  摘要：

  DOI：

  10.1016/s0020-1693(00)91945-5

文献信息

• Reaction of trans-dichloro(ethylene)pyridineplatinum(<scp>II</scp>) complexes with substituted pyridines and ethylene: mechanism of ligand exchange and attack of free base on the co-ordinated olefin. Preparation of two zwitterionic complexes containing platinum–carbon σ-bonds
  作者：Giovanni Natile、Luciana Maresca、Locio Cattalini

  DOI：10.1039/dt9770000651

  日期：——

  Two complexes of formula trans-[Pt(CH2CH2L)CI2L](L = 4-methylpyridine or 3,5-dimethylpyridine) have been prepared by nucleophilic attack of the free amine on the co-ordinated ethylene of trans-[Pt(C2H4)Cl2L]. Such a reaction occurs only with the more basic and less hindered pyridines. The free pyridines also exhibit nucleophilic attack on the metal centre leading to a pyridine-exchange reaction. The

  通过游离胺对反式的配位乙烯的亲核攻击，制备了两种式为反式-[Pt（CH 2 CH 2 L）Cl 2 L]（L = 4-甲基吡啶或3,5-二甲基吡啶）的配合物-[Pt（C 2 H 4）Cl 2 L]。这样的反应仅在碱性较高且受阻较少的吡啶中发生。游离吡啶还对金属中心表现出亲核攻击，从而导致吡啶交换反应。对于所有吡啶，交换过程中活化的自由能为<42 kJ mol –1，其中2,4,6-三甲基吡啶的活化自由能为> 80 kJ mol –1。在游离乙烯的存在下，发生游离烯烃与络合烯烃之间的交换。同样在这种情况下，交换过程是通过游离乙烯攻击金属中心并形成五坐标双（乙烯）过渡态而发生的。该过程的活化自由能为<43 kJ mol –1对于未受阻的吡啶，> 76 kJ mol –1；对于在邻位有两个甲基取代基的吡啶，> 76 kJ mol –1。
• Synthesis and Characterization of Pt(II) Complexes with Pyridyl Ligands: Elongated Octahedral Ion Pairs and Other Factors Influencing ¹H NMR Spectra
  作者：Nerissa A. Lewis、Svetlana Pakhomova、Patricia A. Marzilli、Luigi G. Marzilli

  DOI：10.1021/acs.inorgchem.7b01294

  日期：2017.8.21

  with limited volatility and water solubility, properties typical of 4-Xpy, with X being a moiety targeting drug delivery. Treatment of cis-[PtII(DMSO)2Cl2] (DMSO = dimethyl sulfoxide) with 4-Xpy in acetonitrile allowed isolation of a new series of simple trans-[PtII(4-Xpy)2Cl2] complexes. A side product with very downfield H2/6 signals led to our synthesis of a series of new [PtII(4-Xpy)4]Cl2 salts.

  我们的目标是开发便捷的方法来获得适用于4-取代吡啶（4-Xpy）的反式-[Pt II（4-Xpy）2 Cl 2 ]配合物，该化合物的挥发性和水溶性有限，具有4-Xpy的典型特性，并具有X是靶向药物递送的部分。用4-Xpy在乙腈中处理顺式-[Pt II（DMSO）2 Cl 2 ]（DMSO =二甲基亚砜），可以分离出一系列新的简单的反式-[Pt II（4-Xpy）2 Cl 2 ]复合物。具有低场H2 / 6信号的副产品导致我们合成了一系列新的[Pt II（4-Xpy）4 ] Cl 2盐。对于CDCl 3中的两个系列，随着4-Xpy供体能力从4-CNpy增加到4-Me 2 Npy，H2 / 6Δδ[协调的减去“自由的” 4-Xpy H2 / 6位移]的大小减小。该发现可归因于Pt（II）中心的诱导效应随着4-Xpy供体能力的增强而出现更大的协同降低。[Pt II（4-Xpy）4 ] Cl 2盐在CDCl
• Multinuclear NMR study and crystal structures of complexes of the types cis- and trans-Pt(Ypy)2X2, where Ypy=pyridine derivative and X=Cl and I
  作者：Christian Tessier、Fernande D. Rochon

  DOI：10.1016/s0020-1693(99)00303-5

  日期：1999.11

  and the pyridine ligands do not seem very important. The crystal structures of three dichloro and five diiodo complexes were determined, in an attempt to obtain information on the trans influence of the three ligands. The results have shown that the iodo ligand has the greatest trans influence. Chloro and pyridine ligands seem to have similar trans influence, although, the chloro ligand seems to have

  摘要用光谱方法研究了顺式和反式Pt（Ypy）2X2型配合物，其中Ypy是吡啶的甲基衍生物，X = Cl或I。在195Pt MNR中，在CDCl3中的-1998至-2021 ppm之间观察到顺式二氯化合物，而在-1948至-1973 ppm之间的场中则发现反式化合物。在更高的视野下观察到二碘化合物，对于顺式异构体为-3199至-3288 ppm，对于反式异构体为-3122至-3264 ppm。在1 H NMR中，顺式化合物的3J（195Pt1H）偶联常数（约42 ppm）大于反式异构体的3J（195Pt1H）偶联常数（约33 ppm）。在13 C NMR中，也发现顺式配合物的3J（195Pt for13C）值更大。质子化配体的pKa值似乎对δ（Pt）化学位移有轻微的依赖性。Pt和吡啶配体之间存在π键似乎并不重要。确定了三个二氯和五个二碘配合物的晶体结构，试图获得有关三个配体的反式影响的信
• Stability of [2]Pseudorotaxanes Templated Through Second-Sphere Coordination
  作者：Barry A. Blight、James A. Wisner、Michael C. Jennings

  DOI：10.1021/ic801725u

  日期：2009.3.2

  4-substituted pyridine co-ligand and the subsequent complexation strength in [2]pseudorotaxane formation. These trends also extended to trans-dibromobis(pyridine)palladium(II) (3a-e) and trans- dichlorobis(pyridine)platinum(II) complexes (5a-e) when plotted against σp° values. In addition, solid-state structures of three [2]pseudorotaxanes (1·2h, 1·2i, and 1·5e) were determined by single crystal X-ray

  制备了一系列九种反式-二氯双（吡啶）钯（II）配合物（2a-i），其包含不同的4-取代的吡啶共配体。测量了这些Pd配合物与1之间的缔合常数，并将它们的值相对于相应的σp °值作图。氯化物共配体的氢键受体能力的测量揭示了在给定的4-取代的吡啶共配体的电子感应与随后的[2]假轮烷的形成中的络合强度之间存在线性自由能关系。这些趋势还扩展到反式-二溴双（吡啶）钯（II）（3a-e）和反式相对于σp °值绘制的-二氯双（吡啶）铂（II）配合物（5a-e）。此外，通过单晶X射线衍射确定了三种[2]假轮烷（1·2h，1·2i和1·5e）的固态结构，进一步证实了该模板在形成互穿分子结构中的可行性。
• Synthesis, Characterization, and Reactivity of <i>trans</i>-[PtCl(R‘R‘ ‘SO)(A)₂]NO₃ (R‘R‘ ‘SO = Me₂SO, MeBzSO, MePhSO; A = NH₃, py, pic). Crystal Structure of <i>trans</i>-[PtCl(Me₂SO)(py)₂]⁺
  作者：Ana P. S. Fontes、Åke Oskarsson、Karin Lövqvist、Nicholas Farrell

  DOI：10.1021/ic000107n

  日期：2001.4.1

  4-methylpyridine or picoline (pic)) were prepared for comparison of the chemical reactivity between ammine and pyridine ligands. The X-ray crystal structure determination for trans-[PtCl(Me(2)SO)(py)(2)]NO(3) confirmed the geometry with S-bound Me(2)SO. The crystals are orthorhombic, space group P2(1)2(1)2(1), with cell dimensions a = 7.888(2) A, b = 14.740(3) A, c =15.626(5) A, and Z = 4. The geometry

  反式复合物，例如反式-[PtCl（2）（NH（3））（2）]在历史上一直被认为是无治疗活性的。平面配体如吡啶的使用大大增强了反式几何结构的细胞毒性。反式-[PtCl（R'R''SO）（A）（2）] NO（3）（R'R''SO =取代的亚砜，例如二甲基（Me（2）SO），甲基苄基（MeBzSO ）和甲基苯基亚砜（MePhSO）和A = NH（3），吡啶（py）和4-甲基吡啶或甲基吡啶（pic））的制备，用于比较胺和吡啶配体之间的化学反应性。反式-[PtCl（Me（2）SO）（py）（2）] NO（3）的X射线晶体结构测定证实了S结合的Me（2）SO的几何结构。晶体是正交晶体，空间群P2（1）2（1）2（1），晶胞尺寸为a = 7.888（2）A，b = 14.740（3）A，c = 15.626（5）A和Z = 4。铂原子周围的几何形状为正方形平面，l（Pt-Cl）= 2.304（4）A，l（Pt-S）=