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Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of Chalcogenidoplumbates(II or IV)
Published on: December 29, 2016
Structural insights into heavy chalcogen polycations and their stabilization via (hydrogen)polysulfates
Jan Langwald1, Sergi Burguera2, Antonio Frontera2
1Institute of Inorganic and Materials Chemistry, University of Cologne, Greinstr. 6, 50939 Cologne, Germany. mathias.wickleder@uni-koeln.de.
None:
We report the preparation and characterization of [Se4]2+, [Te4]2+ and [Te6]4+ cations, stabilized as polysulfates, namely [Se4][S2O7], [Se4][HS2O7]2, [Se4][HS3O10]2, [Te4][HS3O10]2, [Te6][HS3O10]4 and [Te6][S4O13]2. In the case of tellurium compounds, this represents the first stabilization and solid-state investigations of the species from chlorosulfuric acid/sulfur trioxide-based media, although the respective colorful solutions are known for over 200 years. The unusual cation-anion interactions were investigated via density functional theory (DFT) calculations, i.e., MEP surface plots, QTAIM and NBO analyses. The non-covalent interactions (chalcogen bonding (ChB)) within the novel species reveal different binding modes, namely bifurcated (Ch⋯O,O or Ch,Ch⋯O) and standard (Ch⋯O) σ-hole interactions. We show that the [Se4]2+ dication exhibits electrophilic duality, engaging in σ- and π-hole interactions, and that the stabilization of polycationic chalcogens with oxoanions is enhanced by auxiliary Ch⋯O contacts.
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