Insertion of CO 2 and CS 2 into Bi-N bonds enables catalyzed CH-activation and light-induced bismuthinidene transfer.

The uptake and release of small molecules continue to be challenging tasks of utmost importance in synthetic chemistry. The combination of such small molecule activation with subsequent transformations to generate unusual reactivity patterns opens up new prospects for this field of research. Here, we report the reaction of CO 2 and CS 2 with cationic bismuth(iii) amides. CO 2 -uptake gives isolable, but metastable compounds, which upon release of CO 2 undergo CH activation. These transformations could be transferred to the catalytic regime, which formally corresponds to a CO 2 -catalyzed CH activation. The CS 2 -insertion products are thermally stable, but undergo a highly selective reductive elimination under photochemical conditions to give benzothiazolethiones. The low-valent inorganic product of this reaction, Bi(i)OTf, could be trapped, showcasing the first example of light-induced bismuthinidene transfer.