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Hydrolysis of cis- and transplatin: structure and reactivity of the aqua complexes in a solvent free environment

机译:顺铂和反铂水解:无溶剂环境中水配合物的结构和反应性

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Singly aquated and diaquated species are key intermediates in the mechanism responsible for the antitumor activity of cisplatin. Aqua complexes [PtX(NH3)2(H2O)]+ (X = Cl, OH), obtained in water by hydrolysis of cisplatin and of the inactive isomer transplatin, are transferred into the gas-phase by electrospray ionization. The so-formed ions, cis- and trans-[PtX(NH3)2(H2O)]+, have been allowed to react with selected ligands, representing platination targets in the biological environment. The reaction kinetics monitored in the gas-phase show consistently higher reactivity for the chloro complexes, [PtCl(NH3)2(H2O)]+, with respect to the hydroxo counterparts, [Pt(OH)(NH3)2(H2O)]+. The latter species, both cis- and trans-isomers, have been assayed by IRMPD spectroscopy in the NH/OH stretching region and their vibrational and geometric features are compared with the ones pertaining to the already described chloro complexes, cis- and trans-[PtCl(NH3)2(H2O)]+.
机译:单水和渗水物种是负责顺铂抗肿瘤活性的机制的关键中间体。水族络合物[PtX(NH 3 2 (H 2 O)] + (X = Cl,OH)在水中通过顺铂和非活性异构体跨铂的水解而获得,然后转移到相通过电喷雾电离。如此形成的离子 cis -和 trans -[PtX(NH 3 2 (H 2 O)] + ,已被允许与选定的配体反应,代表生物环境中的电镀目标。在气相中监测的反应动力学显示出对氯配合物[PtCl(NH 3 2 < / small>(H 2 O)] + ,相对于羟基化合物[Pt(OH )(NH 3 2 (H 2 O)] + 。在NH / OH伸展区中通过IRMPD光谱法测定了后者的 cis -和 trans -异构体,并将它们的振动和几何特征进行了比较。与已经描述的氯配合物 cis -和 trans -[PtCl(NH 3 2 (H 2 O)] +

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