Bismuth in Dynamic Covalent Chemistry: Access to a Bowl-Type Macrocycle and a Barrel-Type Heptanuclear Complex Cation.

Dynamic covalent chemistry (DCvC) is a powerful and widely applied tool in modern synthetic chemistry, which is based on the reversible cleavage and formation of covalent bonds. One of the inherent strengths of this approach is the perspective to reversibly generate novel structural motifs in an operationally simple approach, which are difficult or impossible to access with more traditional methods and require multiple bond cleaving and bond forming steps. To date, these fundamentally important synthetic and conceptual challenges in the context of DCvC have predominantly been tackled by exploiting compounds of lighter p-block elements, albeit heavier p-block elements show low bond dissociation energies and appear to be ideally suited for this approach. Here we show that a dinuclear organometallic bismuth compound, containing BiMe2 groups that are connected by a thioxanthene linker, readily undergoes selective and reversible cleavage of its Bi-C bonds upon exposure to external stimuli. The exploitation of DCvC in the field of organometallic heavy p-block chemistry grants access to unprecedented macrocyclic and barrel-type oligonuclear compounds.