trans-[Pt^II(4-CNpy)₂Cl₂] | 24476-73-1

• 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-[Pt^II(4-CNpy)₂Cl₂]
• 英文别名: trans-[Pt^II(4-cyanopyridine)₂Cl₂]；trans-{Pt(4-CN-py)2Cl2}；Dichloroplatinum;pyridine-4-carbonitrile
• CAS: 24476-73-1
• 化学式: C₁₂H₈Cl₂N₄Pt
• 分子量: 474.208
• InChiKey: JYVUDRBNMHXSFG-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  3.28
• 重原子数：
  19
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  73.4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  potassium cyanide 、 trans-[Pt^II(4-CNpy)₂Cl₂] 以 甲醇 、 水 为溶剂， 生成 {Pt(4-cyanopyridine)(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：

  4-氰基吡啶 、 dichlorobis(dimethyl sulfoxide)platinum(II) 以 乙腈 为溶剂， 以26%的产率得到trans-[Pt^II(4-CNpy)₂Cl₂]
  参考文献：
  名称：

  具有吡啶基配体的Pt（II）配合物的合成和表征：延长的八面体离子对和其他影响1 H NMR光谱的因素

  摘要：

  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

  DOI：

  10.1021/acs.inorgchem.7b01294

文献信息

• The cis- and trans-effects of cyanide in substitution at platinum(II)
  作者：Lucio Cattalini、Francesca Guidi、Martin L. Tobe

  DOI：10.1039/dt9930000233

  日期：——

  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.
• 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