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Five Hypotheses on the Origins of Temperature Dependence of Se NMR Shifts in Diselenides. | LitMetric
Notable thermal shifts in diselenides have been documented in Se NMR for more than 50 years, but no satisfactory explanation has been found. Here, five hypotheses are considered as possible explanations for the large temperature dependence of the Se chemical shifts of diaryl and dialkyl diselenides compared to monoselenides and selenols. Density functional theory calculations are provided to bolster hypotheses and better understand the effects of barrier height and dipole energies. It is proposed that the temperature dependence of diselenide Se NMR chemical shifts is due to rotation around the Se-Se bond and sampling of twisted conformers at higher temperatures. The molecular twisting is solvent dependent; here, DMSO- and toluene- were evaluated. No correlation was established between -substituents on diaryl diselenides and the magnitude of the change in the Se NMR shift (Δδ) with temperature.
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