Abstract

The interaction of mercury(II) dibutyl dithiocarbamate (BuDtc) with [AuCl₄]⁻ anions in 2 M HCl was studied. The heterogeneous reaction of chemisorption binding of gold(III) from the solution leads to heteronuclear Au(III)–Hg(II) pseudo-polymeric complexes of the ionic type: ([Au{S₂CN(C₄H₉)₂}₂]₂[Hg₂Cl₆])_n (I) and ([(C₄H₉)₂NH₂]_0.5[Au{S₂CN(C₄H₉)₂}₂]_1.5[Hg₂Cl₆])_n (II), whose crystal and supramolecular structures were determined by X-ray diffraction analysis (CIF files CCDC nos. 1965151 (I) and 1965152 (II)). The cationic part of each compound is represented by two structurally nonequivalent complex ions [Au{S₂CN(C₄H₉)₂}₂]⁺ (A and B) being conformers. The structure of compound II additionally contains the dibutylammonium cation. In both cases, binuclear [Hg₂Cl₆]^2– is a counterion (centrosymmetric in the structure of compound I and noncentrosymmetric in the structure of compound II). Owing to the secondary interactions Au···S and S···Cl (as well as hydrogen bonds N–H···Cl in compound II), all ionic structural units participate in the construction of pseudo-polymeric cationic and cation-anionic chains, which are combined into a complicatedly organized 2D supramolecular network (in I) or 3D framework (in II). The thermal behavior of compounds I and II was studied by simultaneous thermal analysis. The thermolysis of the complexes is accompanied by the quantitative regeneration of bound gold, liberation of HgCl₂, and partial transformation of the latter into HgS.

中文翻译：

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化学吸附合成，复杂的2D和3D超分子体系结构的自组装（氢键的作用和二次相互作用Au··S和S··Cl的作用）以及拟聚金（III）-汞（II）的热行为二丁基二硫代氨基甲酸酯-氯配合物

摘要

研究了二丁基二硫代氨基甲酸汞（II）（BuDtc）与[AuCl ₄ ] ^-阴离子在2 M HCl中的相互作用。溶液中金（III）的化学吸附结合的异质反应导致离子型杂核Au（III）-Hg（II）假聚合物络合物：（[Au {S ₂ CN（C ₄ H ₉）₂ } ₂ ] ₂ [Hg ₂ Cl ₆ ]）_n（I）和（[（C ₄ H ₉）₂ NH ₂ ] _0.5 [Au {S ₂ CN（C ₄ H₉）₂ } ₂ ] _1.5 [Hg ₂ Cl ₆ ]）_n（II），其晶体和超分子结构是通过X射线衍射分析确定的（CIF文件CCDC编号1965151（I）和1965152（II））。各化合物的阳离子部分由两个结构非等效的复合离子[金{S表示₂ CN（C ₄ H ^ ₉）₂ } ₂ ] ⁺（A和B）是构象异构体。化合物II的结构还含有二丁基铵阳离子。在这两种情况下，双核[Hg ₂ Cl ₆ ] ^2–都是抗衡离子（在化合物I的结构中为中心对称，在化合物II的结构中为非中心对称）。由于Au···S和S···Cl（以及化合物II中的氢键N–H···Cl ）的二次相互作用，所有离子结构单元都参与了假聚合物阳离子和阳离子结构的构建。阴离子链，它们组合成一个复杂组织的2D超分子网络（在I中）或3D框架（在II中）。化合物I和II的热行为通过同时热分析研究。配合物的热解伴随着结合的金的定量再生，HgCl _2的释放以及后者的部分转化为HgS。