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首页> 外文期刊>Chemphyschem: A European journal of chemical physics and physical chemistry >The gas-phase chemistry of cis-diammineplatinum(II) complexes: A joint experimental and theoretical study
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The gas-phase chemistry of cis-diammineplatinum(II) complexes: A joint experimental and theoretical study

机译：顺二氨合铂（II）配合物的气相化学：联合实验和理论研究

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摘要

Prior to reactions with DNA, the anticancer drug cisplatin [Pt-II(NH3)(2)Cl-2] forms a series of solvolysis intermediates by successive replacement of the chloro ligands by water or hydroxyl groups. The bonding of water to Pt-II is weak, and it is easily substituted by donor ligands present in the solution, for example, amines or alcohols. We studied such compounds using high-resolution electrospray mass spectrometry with a linear ion trap and DFT computations. This combination allows for the first time a detailed description of the reactions initiated by the central atom of the complexes. Positively charged cisplatin adducts with primary and secondary alcohols ([Pt-II(NH3)(2)(ROH)Cl](+)) show unexpected reactions when fragmented in a tin-ear ion trap. Either water loss is accompanied by formation of the corresponding carbene complex, or loss of the corresponding aldehyde/ketone leads to the formation of the complex [Pt(NH3)(2)(H-2)Cl](+). Complete loss of the alcohol ligand is not observed for kinetic reasons. A detailed investigation by DFT and molecular dynamics for the cisplatin/methanol complex [Pt-II(NH3)(2)(CH3OH)Cl](+) allowed identification of the reaction mechanisms leading to the observed fragmentation patterns. The initial step for both fragmentation pathways is activation of the alpha-CH bond, and subsequent H transfer within the complex Direct activation of the OH or CO bond is less favorable. Ligands bound to the the Pt-II center such as the chloro ligand con directly catalyze the reaction by intermediate binding of H atoms. Upon collision activation, adducts without an a-H atom such as [Pt(NH3)(2){(CH3)(3)COH}Cl](+) show loss of water or the corresponding alkene.
机译：在与DNA反应之前，抗癌药顺铂[Pt-II（NH3）（2）Cl-2]通过用水或羟基连续取代氯配体形成一系列溶剂分解中间体。水与Pt-II的结合较弱，很容易被溶液中存在的供体配体取代，例如胺或醇。我们使用具有线性离子阱和DFT计算的高分辨率电喷雾质谱对此类化合物进行了研究。这种结合首次使由配合物中心原子引发的反应的详细描述成为可能。当在锡耳离子阱中破碎时，伯醇和仲醇（[Pt-II（NH3）（2）（ROH）Cl]（+））带正电荷的顺铂加合物显示出意外的反应。失水伴随有相应的卡宾配合物的形成，或相应醛/酮的损失导致了[Pt（NH3）（2）（H-2）Cl]（+）配合物的形成。由于动力学原因，未观察到醇配体的完全丧失。通过DFT的详细研究和顺铂/甲醇络合物[Pt-II（NH3）（2）（CH3OH）Cl]（+）的分子动力学研究，可以鉴定导致观察到的断裂模式的反应机理。这两个断裂途径的起始步骤都是激活α-CH键，随后在复合物中进行H转移OH或CO键的直接激活不太理想。结合到Pt-II中心的配体（例如氯配体）通过H原子的中间键合直接催化反应。碰撞激活后，不含a-H原子的加合物，例如[Pt（NH3）（2）{（CH3）（3）COH} Cl]（+），会损失水或相应的烯烃。

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