4-Tetrafluoropyridyl Silver(I), AgC<sub>5</sub>F<sub>4</sub>N, in Redox Transmetalations with Selenium and Tellurium

Abstract

Se­(C<sub>5</sub>F<sub>4</sub>N)<sub>2</sub> and Te­(C<sub>5</sub>F<sub>4</sub>N)<sub>2</sub> were prepared via redox transmetalations of AgC<sub>5</sub>F<sub>4</sub>N and the corresponding elements in good yields. The crystal structures of both derivatives exhibit infinite chains caused by a weak intermolecular contact between the chalcogen and one nitrogen atom with a T-shaped (ψ-pentagonal-bipyramidal) ligand arrangement. Crystallization of both reagents from dimethylsulfoxide gave single crystals of the corresponding 1:1 adducts that crystallize in infinite chains best expressed by the formula [E­(C<sub>5</sub>F<sub>4</sub>N)<sub>2</sub>·(μ-DMSO)]<sub>∞</sub> (E = Se, Te). In these cases, the coordination spheres of selenium and tellurium are square-planar (ψ-octahedral). Similar effects are found in the molecular structures of [Te­(C<sub>5</sub>F<sub>4</sub>N)<sub>2</sub>·TMTU]<sub>∞</sub> and [Te­(C<sub>6</sub>F<sub>5</sub>)<sub>2</sub>·TMTU]<sub>∞</sub> (TMTU = tetramethylthiourea). Differences in the Te–S interatomic distances clearly indicate the C<sub>5</sub>F<sub>4</sub>N ligand being significantly more electron-withdrawing in comparison with the C<sub>6</sub>F<sub>5</sub> group; that is, Te­(C<sub>5</sub>F<sub>4</sub>N)<sub>2</sub> is the stronger Lewis acid

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