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

Robin Weiss, Emmanuel Aubert, Loic Groslambert, Patrick Pale, Victor Mamane

Chemistry (Weinheim an der Bergstrasse, Germany) 2022 May 02

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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 Te4 rectangle through dimer aggregation or a triangular Te3 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 R3 PO as σ-hole acceptors in different solvents. Thus, 125 Te NMR allowed monitoring Te⋅⋅⋅O interaction and delivering association constants (Ka ) for 1 : 1 adducts. The highest value of Ka =90 M-1 was measured for the adduct between ArTeTeAr bearing CF3 groups and Et3 PO in cyclohexane. Notably, by using nBu3 PO, Te⋅⋅⋅O interaction was revealed by 19 F-1 H HOESY showing spatial proximity between CF3 and CH3 of nBu3 PO. © 2022 Wiley-VCH GmbH.

Citation

Robin Weiss, Emmanuel Aubert, Loic Groslambert, Patrick Pale, Victor Mamane. Chalcogen Bonding with Diaryl Ditellurides: Evidence from Solid State and Solution Studies. Chemistry (Weinheim an der Bergstrasse, Germany). 2022 May 02;28(25):e202200395