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Abstract While SbCl₃is typically inert toward oxidation byortho‐quinones, we useo‐chloranil to show that the outcome of such reactions may be altered by the presence of a donor such as triphenylphosphine oxide, which readily traps the SbCl₃(cat^Cl) synthon (cat^Cl = tetrachlorocatecholate) in the form of the corresponding adduct Ph₃PO→SbCl₃(cat^Cl). The same reaction in the presence of a chloride salt affords the corresponding antimonate anion [Cl₄Sb(cat^Cl)]⁻. Computational studies indicate that the putative SbCl₃(cat^Cl) synthon has a higher chloride ion affinity than SbCl₅, suggesting significant Lewis acidity. This property is further demonstrated by the use of the SbCl₃/o‐chloranil system for both THF polymerization and a Friedel–Crafts‐type alkylation of benzene using 1‐fluorooctane. Finally, the reaction ofE‐stilbene witho‐chloranil in the presence of SbCl₃affords the corresponding benzodioxene, suggesting that SbCl₃may also operate as a redox‐active catalyst. 

Abstract Our interest in the design of heavy pnictogen‐based Lewis acids for anion trafficking across biological membrane mimics has led us to investigate trivalent bismuthenium cations as chloride anion transporters. Here, we describe two chlorodiarylbismuthines, elaborated on aperi‐substituted naphthalene backbone and stabilized by an adjacent thio‐ or seleno‐ether functionality that engages the bismuth center in a Ch→Bi interaction (Ch=chalcogen). These new derivatives are stable in aqueous environment and readiliy transport chloride anions across the membrane of phospholipid‐based vesicles loaded with KCl. In addition to establishing the use of such motifs in anion transport, this investigation shows that the Lewis acidity, lipophilicity, and thus chloride transport properties depend on the nature of the chalcogen.