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 in an operationally simple approach novel structural motifs that 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, even though 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