Catalytic oxidative coupling promoted by bismuth TEMPOxide complexes

Bismuth(III) TEMPOxide compounds have been synthesized from the coupling of Bi(II) species with the TEMPO˙ radical. The steric profile of the supporting bis(amido)disiloxane ligand promotes different fluxional behaviour in solution, and DFT calculations suggest variation in the Bi–O bond character. These compounds are active catalysts for oxidative coupling of TEMPO and silane substrates, believed to proceed via metathesis of Bi–O and Si–H bonds followed by decomposition of bismuth-hydride intermediate species.