Synthesis, structure and chemical reactivity of pyridine-2-thione/pyrimidine-2-thione derivatives of mercury (II) and silver(I)

IF 2.7 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta Pub Date : 2025-06-02 DOI:10.1016/j.ica.2025.122798

Yachika Teji , Kashima Soni , Tarlok S. Lobana , Ray J. Butcher

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Abstract

A reaction of mercury (II) iodide with pyridine-2-thione (pytH) in 1: 2 (M: L) molar ratio in a CH₃CN-MeOH mixture yielded a light brown compound, [HgI₂(κ¹S-pytH)₂] 1. A similar reaction with pyrimidine-2-thione (pymtH) also formed pale yellow crystals of [HgI₂(κ¹S-pymtH)₂] 2. Further, mercury(II) bromide with pytH in CH₃CN in presence of DMF yielded a de-brominated compound [Hg(κ¹S-pyt)₂] 3. Compounds 1 and 2 have distorted tetrahedral geometry, while compound 3 has linear geometry. In case of silver, the reaction of AgBr with pytH in the presence of excess PPh₃, designed for the preparation of a mononuclear compound, [AgBr(pytH)(PPh₃)₂], rather yielded a dinuclear compound, [Ag₂Br₂(μ-S-pytH)₂(PPh₃)₂] 4. Finally, AgNO₃ with pymtH and PPh₃ in a 1: 1: 2 M ratio has formed the ionic complex, [Ag(κ¹S-pymtH)(PPh₃)₂](NO₃) 5, with a distorted trigonal planar cation. The presence of DMF solvent under hot experimental conditions favoured de-halogenation of mercury halides (Br, Cl), and in case of silver, the size of the anions affected the nature of the silver products.

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汞（II）和银(I)的吡啶-2-硫酮/嘧啶-2-硫酮衍生物的合成、结构和化学反应性

在CH3CN-MeOH混合物中，碘化汞（II）与吡啶-2-硫酮（pytH）以1:2 （M: L）的摩尔比反应生成浅棕色化合物[HgI2(κ1S-pytH)2] 1。与嘧啶-2-硫酮（pymtH）的类似反应也形成了[HgI2(κ1S-pymtH)2] 2的淡黄色晶体。此外，在DMF的存在下，CH3CN中含有pytH的溴化汞（II）生成了一种去溴化化合物[Hg(κ1S-pyt)2] 3。化合物1和2具有扭曲的四面体几何，而化合物3具有线性几何。以银为例，在过量PPh3存在的情况下，AgBr与pytH的反应本来是为制备单核化合物[AgBr(pytH)(PPh3)2]而设计的，结果生成了双核化合物[Ag2Br2(μ-S-pytH)2(PPh3)2] 4。最后，AgNO3与pymtH和PPh3以1:1:1:2 M的比例形成具有扭曲三角形平面阳离子的离子配合物[Ag(κ1S-pymtH)(PPh3)2](NO3) 5。DMF溶剂在热实验条件下的存在有利于卤化汞（Br, Cl）的脱卤化，而对于银，阴离子的大小影响银产物的性质。

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来源期刊

Inorganica Chimica Acta 化学-无机化学与核化学

CiteScore

6.00

自引率

3.60%

发文量

440

审稿时长

35 days

期刊介绍： Inorganica Chimica Acta is an established international forum for all aspects of advanced Inorganic Chemistry. Original papers of high scientific level and interest are published in the form of Articles and Reviews. Topics covered include: • chemistry of the main group elements and the d- and f-block metals, including the synthesis, characterization and reactivity of coordination, organometallic, biomimetic, supramolecular coordination compounds, including associated computational studies; • synthesis, physico-chemical properties, applications of molecule-based nano-scaled clusters and nanomaterials designed using the principles of coordination chemistry, as well as coordination polymers (CPs), metal-organic frameworks (MOFs), metal-organic polyhedra (MPOs); • reaction mechanisms and physico-chemical investigations computational studies of metalloenzymes and their models; • applications of inorganic compounds, metallodrugs and molecule-based materials. Papers composed primarily of structural reports will typically not be considered for publication.