Thiazolium Salts as Chalcogen Bond Donors

The nitrogen atom is commonly considered to be the positive site in thiazolium cations. Counterintuitively, shortest cation···anion contacts salts and their benzoderivatives involve sulfur atom. geometric features of these allow for rationalization as charge assisted chalcogen bonds (ChBs). Analyses Cambridge Structural Database calculation surface electrostatic potential benzo[d]thiazolium cations support this rationalization. relevance impact general tendency derivatives function ChB donors are exemplified by ChBs short 87% sum van der Waals radii involved atoms thiamine monophosphate, a key compound human metabolism, two used organocatalysts.