Kinetic investigation of reactions of a 3-arylidene-2-thiohydantoin derivative with palladium (II) salts

IF 1 4区化学 Q4 CHEMISTRY, MULTIDISCIPLINARY

Journal of The Serbian Chemical Society Pub Date : 2023-01-01 DOI:10.2298/jsc230626052s

P. Stanić, Darko P Ašanin, T. Soldatović, Marija D. Živković

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引用次数: 0

Abstract

1H NMR spectroscopy was used to monitor the reactions of an arylidene 2-thiohydantoin derivative, 3-((phenylmethylene)amino)-2-thioxo-4- imidazolidinone (3), with PdCl2, cis-[PdCl2(dmso-S)2] and K2[PdCl4] in DMSO-d6 in order to elucidate the reaction kinetics and mechanism. The 2-thiohydantoin derivative 3 formed cis-[Pd(3-N,S)(dmso-S)2]+ complex (5) in reactions with PdCl2 and cis-[PdCl2(dmso-S)2], while no reaction with K2[PdCl4] was observed. A two-step mechanism for the reactions of 3 with PdCl2 and cis-[PdCl2(dmso- S)2] is proposed, in which fast coordination to the side chain nitrogen occurs in the first step, while chelation and coordination to the sulfur atom in the 2- thiohydantoin ring is the second, slower, rate-determining step. The reaction rate constants were calculated and reactivities of the 2-thiohydantoin derivative 3 towards the palladium(II) salts were compared and discussed. Reaction of 3 with cis-[PdCl2(dmso-S)2] was faster than with PdCl2. The investigated palladium(II) salts also react with the solvent, DMSO-d6, and the influence of these side reactions on the outcome and kinetics of the 2-thiohydantoin derivative complexation reaction is discussed in detail. The obtained results of this study can have an impact in explanation of the coordination behavior of antitumor active palladium(II) and platinum(II) complexes

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3-芳基醚-2-硫代氢酰英衍生物与钯盐反应动力学研究

利用核磁共振氢谱(1H NMR)对芳基2-硫代海因衍生物3-((苯基亚甲基)氨基)-2-硫代-4-咪唑烷酮(3)在DMSO-d6中与PdCl2、顺式-[PdCl2(dmso-S)2]和K2[PdCl4]的反应进行了监测，以阐明反应动力学和机理。2-硫代海因衍生物3与PdCl2和顺式-[PdCl2(dmso-S)2]反应形成顺式-[Pd(3- n,S)(dmso-S)2]+络合物(5)，未与K2[PdCl4]反应。提出了3与PdCl2和顺式-[PdCl2(dmso- S)2]反应的两步机制，其中与侧链氮的快速配位发生在第一步，而与2-硫代氢醛酸环中的硫原子的螯合和配位是第二步，较慢，决定速率的步骤。计算了反应速率常数，并比较讨论了2-硫代海因衍生物3对钯(II)盐的反应活性。3与顺式-[PdCl2(dmso-S)2]的反应比与PdCl2的反应快。所研究的钯(II)盐还与溶剂DMSO-d6发生反应，并详细讨论了这些副反应对2-硫代海因衍生物络合反应的结果和动力学的影响。本研究获得的结果可以对解释抗肿瘤活性钯(II)和铂(II)配合物的配位行为产生影响

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来源期刊

Journal of The Serbian Chemical Society 化学-化学综合

CiteScore

1.80

自引率

0.00%

发文量

审稿时长

1 months

期刊介绍： The Journal of the Serbian Chemical Society -JSCS (formerly Glasnik Hemijskog društva Beograd) publishes articles original papers that have not been published previously, from the fields of fundamental and applied chemistry: Theoretical Chemistry, Organic Chemistry, Biochemistry and Biotechnology, Food Chemistry, Technology and Engineering, Inorganic Chemistry, Polymers, Analytical Chemistry, Physical Chemistry, Spectroscopy, Electrochemistry, Thermodynamics, Chemical Engineering, Textile Engineering, Materials, Ceramics, Metallurgy, Geochemistry, Environmental Chemistry, History of and Education in Chemistry.