{(1,5-diamino-3-aza-pentane)(bromo)palladium(II)} bromide | 92306-24-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: {(1,5-diamino-3-aza-pentane)(bromo)palladium(II)} bromide
• 英文别名: (diethylenetriamine)palladium(II) dibromide；[(dien)PdBr]Br；[PdBr(dien)]Br
• CAS: 92306-24-6
• 化学式: Br*C₄H₁₃BrN₃Pd
• 分子量: 369.395
• InChiKey: KHVVSVQHMVPGOE-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  肌苷 、 {(1,5-diamino-3-aza-pentane)(bromo)palladium(II)} bromide 以 水 为溶剂， 生成 Pd(H2NCH2CH2NHCH2CH2NH2)(inosine)(2+)
  参考文献：
  名称：

  Segun, J.-Y.; Zador, M., Inorganica Chimica Acta, 1976, vol. 20, p. 203 - 206

  摘要：

  DOI：

文献信息

• The displacement of the heterocyclic base R-py from [Pd(dien)(R-py)]2+(dien = 1,5-diamino-3-azapentane, R-py = 4-chloropyridine or 4-aminopyridine) by water in acid and basic solution and by chloride. The involvement of a stable five-co-ordinate species
  作者：Luciano Canovese、Lucio Cattalini、Paolo Uguagliati、Martin L. Tobe

  DOI：10.1039/dt9900003271

  日期：——

  kinetics of displacement of R-py from the [Pd(dien)(R-py)]2+ cation in acid and basic solution in the absence and presence of chloride ions are reported. In acid solution the rate of displacement of 4-chloropyridine is independent of [H+] but that for 4-aminopyridine is acid catalysed, the pyridylammonium ligand being a much better leaving group. In basic solution, the rate of displacement of 4-chloropyridine

  报告了在不存在和存在氯离子的情况下，R-py从[Pd（dien）（R-py）] 2+阳离子在酸和碱性溶液中置换的动力学。在酸性溶液中，4-氯吡啶的置换速率与[H + ]无关，但对于4-氨基吡啶则是酸催化的，吡啶鎓铵配体是一个更好的离去基团。在碱性溶液中，4-氯吡啶的置换速率遵循速率方程10 3 k obs。= 8.7 + 11.5 [OH – ] + 122 [OH – ] 2 s –1，而4-氨基吡啶配合物的值独立于[OH – ]。[Pd（dien）（4Cl-py）] 2+之间的反应Cl-和-导致快速形成稳定的中间物种，该中间物种与[Pd（dien）Cl] +和4Cl-py处于平衡状态。在4-氨基吡啶络合物的反应中没有观察到这样的中间体，该4-氨基吡啶络合物通过在平面-平面络合物中取代的正常途径失去了配体。在存在酸的情况下，Cl –的进入是不可逆的，并且两种底物均恢复为配体取代的经典机理。
• The appearance of a stable intermediate in some substitution reactions of (1,5-diamino-3-azapentane)pyridinepalladium(II) perchlorate
  作者：Luciano Canovese、Lucio Cattalini、Paolo Uguagliati、Martin L. Tobe

  DOI：10.1039/dt9900000867

  日期：——

  =(2.33 ± 0.1)+(6.3 ± 0.8)[OH–]+(8.05 ± 0.9)[OH–]2 s–1 at 25 °C, I= 1.0 mol dm–3. Chloride ions interact readily with the complex but the change in absorbance, while qualitatively consistent with the displacement of pyridine by Cl–, can only be accounted for if an intermediate species containing both chloride and pyridine is formed in significant quantity. The kinetics and equilibria of the formation

  研究了水溶液中[Pd（dien）（py）] 2+（dien = 1,5-二氨基-3-氮杂戊烷）中吡啶（py）可逆置换的动力学和平衡。在酸性溶液中，该反应是可逆的，并且在25°C下溶剂化速率常数=（2.5±0.1）×10 –3 s –1与[H + ]无关。在氢氧化物过量的情况下，反应完成，[OH – ]的依存关系为10 3 k obs。=（2.33±0.1）+（6.3±0.8）[OH – ] +（8.05±0.9）[OH – ] 2 s –1在25°C，I = 1.0 mol dm –3。氯离子与复合物，但在吸光度的变化容易地进行交互，而与吡啶的经Cl位移定性一致- ，只能占如果显著量形成含有二者酰氯和吡啶的中间物种。在中性水溶液中，在25°C，I = 1.0 mol dm –3的条件下，研究了该物种形成的动力学和平衡。讨论了该中间体的性质。
• Predicting speciation in the multi-component equilibrium self-assembly of a metallosupramolecular complex
  作者：Thomas M. Fyles、Christine C. Tong

  DOI：10.1039/b613758j

  日期：——

  A practical method to predict the speciation in a multi-component equilibrium self-assembly process has been developed and applied to the formation of the square macrocyclic complex formed from (ethylenediamine)Pd(II) and 4,4′-bipyridyl. The method is based on an additive free energy approach that derives the cumulative formation constants of all 56 species at equilibrium from a set of five pair-wise interactions. Estimates for the required values of the pair-wise interactions were derived from potentiometric titration of (ethylenediamine)Pd(II) and 3-phenylpyridine, and from (diethylenetriamine)Pd(II) and 4,4′-bipyridyl systems. The method calculates the equilibrium speciation as a function of reactant concentrations and pH and produces a map of the range of compositions in which the square complex and competing species are dominant. The predictions of the method closely correlate with available experimental data.

  我们开发了一种实用的方法来预测多组分平衡自组装过程中的种类，并将其应用于（乙二胺）钯（II）和 4,4′-联吡啶形成的方形大环配合物。该方法基于自由能加成法，通过一组五对相互作用推导出所有 56 个物种在平衡状态下的累积形成常数。通过对（乙二胺）Pd(II)和 3-苯基吡啶以及（二乙烯三胺）Pd(II)和 4,4′-联吡啶体系进行电位滴定，得出了成对相互作用所需数值的估计值。该方法计算了作为反应物浓度和 pH 值函数的平衡标示，并绘制了方形络合物和竞争物种占主导地位的成分范围图。该方法的预测结果与现有实验数据密切相关。
• 1-Methylisocytosine as a ligand for (dien)MII (M=Pt, Pd) and Pt-promoted deamination to 1-methyluracil
  作者：Deepali Gupta、Michael Roitzsch、Bernhard Lippert

  DOI：10.1016/j.ica.2006.12.022

  日期：2007.5

  Abstract 1-Methylisocytosine (1-MeIC) can be protonated at the endocyclic N(3) position (pKa of 1-MeICH+, 4.02 ± 0.04) or complexed at this position with (dien)MII (M = Pt, Pd). X-ray crystal structures of the protonated species 1 as well as the Pd (2) and Pt (3) complexes are reported, and gas phase structures of the cation 2 and 3 have been calculated by ab initio methods. These results are compared

  摘要1-甲基异胞嘧啶（1-MeIC）可以在环内N（3）位置（pKa为1-MeICH +，4.02±0.04）质子化，或在该位置与（dien）MII（M = Pt，Pd）络合。报告了质子化物种1以及Pd（2）和Pt（3）配合物的X射线晶体结构，并通过从头算方法计算了阳离子2和3的气相结构。将这些结果与X射线晶体学的结果进行比较。在高pH下，Pt配合物3经历环外N（2）H2基团脱氨成1-甲基尿嘧啶配合物的过程。与1-甲基胞嘧啶（1-MeC）的情况相比，（dien）PtII的加速作用不那么明显。
• Complex Formation of Isocytosine Tautomers with Pd^II and Pt^II
  作者：Deepali Gupta、Markus Huelsekopf、Marta Morell Cerdà、Ralf Ludwig、Bernhard Lippert

  DOI：10.1021/ic0353965

  日期：2004.5.1

  Isocytosine (ICH) exists in solution as two major tautomers, the keto form with N1 carrying a proton (1a) and the keto form with N3 being protonated (1b). In water, 1a and 1b exist in equilibrium with almost equal amounts of both forms present. Reactions with a series of Pd-II and Pt-II am(m)ine species such as (dien)Pd-II, (dien)Pt-II, and trans-(NH3)(2)Pt-II reveal, however, a distinct preference of these metals for the N3 site, as determined by H-1 NMR spectroscopy. Individual species have been identified by the pD dependence of the ICH resonances. pK(a) values (calculated for H2O) for deprotonation of the individual tautomers complexes are 6.5 and 6.4 for the N3 linkage isomers of dienPd(II) and dienPt(II), respectively, as well as 6.2 and 6.0 for the N1 linkage isomers. The dimetalated species [(dienM)(2)(IC-N1,N3)](3+) (M = Pd-II or Pt-II) are insensitive over a wide range of pD. The crystal structure analysis of [(dien)Pd(ICH-N3)](NO3)(2) is reported. Ab initio calculations have been performed for tautomer compounds of composition [(NH3)(3)Pt(ICH)](2+), cis- and trans-[(NH3)(2)PtCl(ICH)](+), as well as trans-[(NH3)(2)Pt(ICH)(2)](2+). Without exception, N3 linkage isomers are more stable, in agreement with experimental findings. As to the reasons for this binding preference, an NBO (natural bond orbital) analysis for [(NH3)(3)Pt(ICH-N3)](2+) strongly suggests that intramolecular hydrogen bonding between trans-positioned NH3 ligands and the two exocyclic groups of the ICH is of prime importance. The calculations furthermore show a marked pyramidalization of the NH2 group of ICH in the complex once the heterocyclic ligand forms a dihedral angle <90degrees with the Pt coordination plane.