trans-Pt(2-methylpyridine)2Cl2 | 52613-97-5

• 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-Pt(2-methylpyridine)2Cl2
• 英文别名: trans-[Pt(2-picoline)2Cl2]；Dichloroplatinum;2-methylpyridine
• CAS: 52613-97-5
• 化学式: C₁₂H₁₄Cl₂N₂Pt
• 分子量: 452.243
• InChiKey: VLYFSLAEQRERHM-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：

  trans-Pt(2-methylpyridine)2Cl2 在 HCl 作用下， 以 水 为溶剂， 生成 trans-[Pt(OH2)2((15)NH3)(2-picoline)](2+)
  参考文献：
  名称：

  顺铂和反铂（II）二胺类抗癌化合物的化学对比：甲基吡啶配合物的水解研究。

  摘要：

  顺式[PtCl2（NH3）（2-甲基吡啶）]（AMD473）目前正在作为抗癌药物进行临床试验。反式异构体AMD443（1）在多种癌细胞系中也具有细胞毒性。反式异构体（1）的X射线晶体结构表明，与几乎垂直（103度）的顺式异构体相反，吡啶环相对于铂方平面倾斜69度。在3-picoline（2）和4-picoline（3）反式异构体中，环分别倾斜58度/ 60度（2个分子/晶胞）和56度。水解可能是这些复合物的细胞内活化和抗癌作用机制中的重要步骤。第一步水解即使在277 K时也相对较快，速率常数（由1H，15N NMR确定）为k1 = 2.6 x 10（-5）s（-1），12.7 x 10（-5）s（-1） ）和5。2 x 10（-5）s（-1）（I = 0.1 M）分别形成1-3的一元水合物。尽管3的水解比2慢，但水解程度更大。在277 K时，三种配合物均未见透水配合物形成，在310 K时，

  DOI：

  10.1021/ic050763t
• 作为产物：
  描述：

  碳酸甲丙酯 、 potassium tetrachloroplatinate(II) 以 甲醇 、 水 为溶剂， 生成 trans-Pt(2-methylpyridine)2Cl2
  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

文献信息

• Synthesis and NMR characterization of the novel mixed-ligand Pt(II) complexes cis- and trans-Pt(Ypy)(pyrimidine)Cl2 and trans,trans-Cl2(Ypy)Pt(μ-pyrimidine)Pt(Ypy)Cl2 (Ypy=pyridine derivative)
  作者：Fernande D. Rochon、Majd Fakhfakh

  DOI：10.1016/j.ica.2008.07.003

  日期：2009.4

  signals of the cis monomers were found at slightly higher fields than those of the corresponding trans isomers. The δ ( 195 Pt) of the dimers were found close to those of the trans monomers. The NMR results were interpreted in relation to the solvent effect, which seems important in these complexes. The coupling constants J ( 195 Pt– 1 H) and J ( 195 Pt– 13 C) are larger in the cis geometry. The crystal

  摘要合成了Ypy =吡啶衍生物和pm =嘧啶的顺式和反式-Pt（Ypy）（pm）Cl 2型混合配体配合物，并通过红外光谱和多核（195 Pt，1 H和13 C ）磁共振波谱学。顺式化合物是由K [Pt（Ypy）Cl 3]与嘧啶（1：1比例）在水中反应制得的，而大多数反式异构体是由顺式化合物的异构化合成的。顺式异构体不能与邻位含有两个–CH 3基团的Ypy配体分离。当以Pt∶pm比＝ 2∶1进行K [Pt（Ypy）Cl 3]与嘧啶的水反应时，形成了嘧啶桥连的双核物质。只有最稳定的反式-反式异构体才能分离出纯净的。在红外光谱中，顺式单体显示出两个ν（Pt–Cl）谱带，反式单体和二聚体仅显示一个ν（Pt–Cl）谱带。发现顺式单体的195 Pt NMR信号的场强于相应的反式异构体的场。发现二聚体的δ（195 Pt）接近反式单体的δ。解释了NMR结果与溶剂效应的关系，这在这些配合物中似乎很重要。在顺式几何中，耦合常数J（195
• Nucleophilic displacement of the chelating bis(sulfoxide) from cis-[meso-1,2-bis(phenylsulfinyl)ethane]dichloroplatinum(II) and cis-[rac-1,2-bis(phenylsulfinyl)ethane]dichloroplatinum(II)
  作者：Lucio Cattalini、Giampaolo Marangoni、Gianni Michelon、Gino Paolucci、Martin L. Tobe

  DOI：10.1021/ic50215a017

  日期：1981.1
• Trans platinum(II) complexes with pyridine and substituted pyridines
  作者：Laurence K. Thompson

  DOI：10.1016/s0020-1693(00)91945-5

  日期：1980.1
• Mostafa Hossain; Ogura, Indian Journal of Chemistry, Section A: Inorganic, Physical, Theoretical and Analytical, 1996, vol. 35, # 5, p. 373 - 378
  作者：Mostafa Hossain、Ogura

  DOI：——

  日期：——
• 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.