Bednarek Elzbieta, Sitkowski Jerzy, Kawecki Robert, Kozerski Lech, Bocian Wojciech, Pazderski Leszek, Priebe Waldemar
National Medicines Institute, Chełmska 30/34, 00-725, Warsaw, Poland.
Dalton Trans. 2008 Aug 21(31):4129-37. doi: 10.1039/b805572f. Epub 2008 Jul 8.
Pd(II) and Pt(II) chloride complexes with LL = methyl cis-3,4-diamino-2,3,4,6-tetradeoxy-alpha-l-lyxo-hexopyranoside of the formulae [Pd(LL)Cl(2)] and [Pt(LL)Cl(2)], 1, were studied by (1)H, (2)H, (13)C, (15)N and (195)Pt NMR spectroscopy. These techniques were applied for characterization of the structure and ligand exchange dynamics, in case of diastereomeric species formed from 1 in DMSO-d(6), DMSO-h(6) and H(2)O; their general formula was Pt(LL)XY (X = Cl, Y = DMSO-d(6), 2a; X = DMSO-d(6), Y = Cl, 2b; X = Cl, Y = DMSO-h(6), 2a'; X = DMSO-h(6), Y = Cl, 2b'; X = Cl, Y = H(2)O, 3a; X = H(2)O, Y = Cl, 3b). Their theoretical structures and NMR parameters, calculated at the level of DFT approach, were also presented and compared to the experimental data. The model complex [Pt(trans-diaminocyclohexane)Cl(2)], 4, was studied as well. To the best of our knowledge, this work is the first account dealing with the detailed analysis of structure and dynamics of ligand exchange processes in organic solvents and water, performed for a PtCl(2) complex containing a diaminosugar moiety. The kinetic behavior of the studied coordination compounds suggests that some of them may be potentially active in bioassays against cancer cells. Compound 1 exhibits noticeable versatile ligand exchange possibilities in DMSO and H(2)O. Particularly, it undergoes solvolysis in DMSO-d(6), exchanging one chloride atom and yielding two diastereomers 2a and 2b; the former, being the kinetically favored species, has the DMSO-d(6) ligand syn to the N(3) atom. The lyophilisate of the respective 2a + 2b mixture, earlier equilibrated in DMSO-d(6), after dissolving in H(2)O yields only the latter isomer, which is thermodynamically favored. The solvolysis of 1 in H(2)O yields instantaneously two diastereomeric monoaquated species, 3a and 3b, amounting to 10% of each.
对式为[Pd(LL)Cl₂]和[Pt(LL)Cl₂]（1）的钯（II）和铂（II）氯化物配合物与LL = 甲基顺式-3,4-二氨基-2,3,4,6-四脱氧-α-L-来苏糖己吡喃糖苷进行了¹H、²H、¹³C、¹⁵N和¹⁹⁵Pt核磁共振光谱研究。这些技术用于表征结构和配体交换动力学，研究对象是在氘代二甲亚砜（DMSO-d₆）、普通二甲亚砜（DMSO-h₆）和水中由1形成的非对映异构体物种；它们的通式为[Pt(LL)XY]⁺（X = Cl，Y = DMSO-d₆，2a；X = DMSO-d₆，Y = Cl，2b；X = Cl，Y = DMSO-h₆，2a'；X = DMSO-h₆，Y = Cl，2b'；X = Cl，Y = H₂O，3a；X = H₂O，Y = Cl，3b）。还给出了在密度泛函理论（DFT）方法水平上计算得到的它们的理论结构和核磁共振参数，并与实验数据进行了比较。对模型配合物[Pt(反式-二氨基环己烷)Cl₂]（4）也进行了研究。据我们所知，这项工作是首次对含有二氨基糖部分的PtCl₂配合物在有机溶剂和水中的配体交换过程的结构和动力学进行详细分析。所研究的配位化合物的动力学行为表明，其中一些可能在针对癌细胞的生物测定中具有潜在活性。化合物1在DMSO和H₂O中表现出明显的多种配体交换可能性。特别是，它在DMSO-d₆中发生溶剂解，交换一个氯原子并产生两种非对映异构体2a和2b；前者是动力学上有利的物种，其DMSO-d₆配体与N(3)原子顺式。各自的2a + 2b混合物的冻干物，之前在DMSO-d₆中达到平衡，溶解在H₂O中后只产生后者异构体，后者是热力学上有利的。1在H₂O中的溶剂解瞬间产生两种非对映异构的单水合物种3a和3b，各占10%。
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