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Article Dans Une Revue Chemistry - A European Journal Année : 2022

Chalcogen Bonding with Diaryl Ditellurides: Evidence from Solid State and Solution Studies.

Résumé

The chalcogen bonding (ChB) ability of Te is studied in symmetrical diaryl ditellurides ArTeTeAr. Among the two Te σ-holes, the one along the less polarized Te-Te bond was calculated as the more electropositive. This counter-intuitive situation is due to the hyperconjugation contribution from Te lone pair to the σ* of the adjacent Te which coincides with σ-hole along the more polarized Te-Ar bond. ArTeTeAr showed notable structural features in the solid state as a result of intermolecular Te···Te ChB, such as a Te 4 rectangle through dimer aggregation or a triangular Te 3 motif, where one Te interacts with both Te atoms of a neighboring molecule through both its σ-hole and lone pair, in a slightly frustrated geometry. Lewis acidity of ArTeTeAr was also evaluated by NMR with R 3 PO as σ-hole acceptors in different solvents. Thus, 125 Te NMR allowed monitoring Te···O interaction and delivering association constants ( K a ) for 1:1 adducts. The highest value of K a = 90 M -1 was measured for the adduct between ArTeTeAr bearing CF 3 groups and Et 3 PO in cyclohexane. Notably, by using n Bu 3 PO, Te···O interaction was revealed by 19 F- 1 H HOESY showing spatial proximity between CF 3 and CH 3 of n Bu 3 PO.
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Dates et versions

hal-03615217 , version 1 (30-03-2022)

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Robin Weiss, Emmanuel Aubert, Loic Groslambert, Patrick Pale, Victor Mamane. Chalcogen Bonding with Diaryl Ditellurides: Evidence from Solid State and Solution Studies.. Chemistry - A European Journal, inPress, ⟨10.1002/chem.202200395⟩. ⟨hal-03615217⟩
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