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<p>The speciation of Ag<sup>+</sup> in DMSO remains a challenging question due to the formation of equilibrated polynuclear species of unknown nature. This contribution illustrates a possible presence of [Ag<sub>4</sub>(µ<sub>2</sub>-DMSO)<sub>6</sub>(DMSO)<sub>2</sub>]<sup>4+</sup> polynuclear moiety as a component of Ag<sup>+</sup> speciation in DMSO solution. This cation was isolated in the solid state by the assist of [SiW<sub>12</sub>O<sub>40</sub>]<sup>4–</sup> as a counter anion. The dried crystals of [Ag<sub>4</sub>(µ<sub>2</sub>-DMSO)<sub>6</sub>(DMSO)<sub>2</sub>][SiW<sub>12</sub>O<sub>40</sub>]·3DMSO·0.7H<sub>2</sub>O (<b>1</b>) have been characterized by single crystal X-ray diffraction (SCXRD), powder X-ray diffraction (PXRD), FT-IR and TGA. Argentophilic interactions in the cation were studied by quantum-chemical calculations, revealing non-uniform Ag–O interaction of the “central” DMSO ligand with three closest surrounding Ag atoms. The solutions of <b>1</b> in CH<sub>3</sub>CN were studied by high performance liquid chromatography coupled with ICP (HPLC-ICP-AES) and electrochemistry. The results indicate that the [Ag<sub>4</sub>(µ<sub>2</sub>-DMSO)<sub>6</sub>(DMSO)<sub>2</sub>]<sup>4+</sup> complex undergoes speciation in the solution with the formation of several silver containing species, whose chromatographic indication is possible owing to slow exchange kinetics between DMSO and CH<sub>3</sub>CN ligands. Such mixed ligand complexes are quite unusial and need further characterization.</p>

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Capture of [Ag4(µ2-DMSO)6(DMSO)2]4+ by Silicotungstate: Structural, Solution and Computational Studies

  • 期刊论文

  • 发表日期：

    2026年2月20日

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  • Victoria V. Volchek,
  • Vasily V. Kokovkin,
  • Veronica S. Sulyaeva,
  • Taisiya S. Sukhikh,
  • Ilya V. Korolkov,
  • Maxim N. Sokolov,
  • Pavel A. Abramov

摘要

The speciation of Ag+ in DMSO remains a challenging question due to the formation of equilibrated polynuclear species of unknown nature. This contribution illustrates a possible presence of [Ag4(µ2-DMSO)6(DMSO)2]4+ polynuclear moiety as a component of Ag+ speciation in DMSO solution. This cation was isolated in the solid state by the assist of [SiW12O40]4– as a counter anion. The dried crystals of [Ag4(µ2-DMSO)6(DMSO)2][SiW12O40]·3DMSO·0.7H2O (1) have been characterized by single crystal X-ray diffraction (SCXRD), powder X-ray diffraction (PXRD), FT-IR and TGA. Argentophilic interactions in the cation were studied by quantum-chemical calculations, revealing non-uniform Ag–O interaction of the “central” DMSO ligand with three closest surrounding Ag atoms. The solutions of 1 in CH3CN were studied by high performance liquid chromatography coupled with ICP (HPLC-ICP-AES) and electrochemistry. The results indicate that the [Ag4(µ2-DMSO)6(DMSO)2]4+ complex undergoes speciation in the solution with the formation of several silver containing species, whose chromatographic indication is possible owing to slow exchange kinetics between DMSO and CH3CN ligands. Such mixed ligand complexes are quite unusial and need further characterization.