Activation and Catalytic Degradation of SF₆ and PhSF₅ at a Bismuth Center

In this work, we report the catalytic degradation of SF₆ and PhSF₅ using N,C,N pincer bismuthinidene complexes (1 and 5). Exposure of SF₆ and PhSF₅ to 1 results in the reduction of the S(VI) substrates and concomitant formation of Bi(III) and Bi(II) compounds, which were isolated and characterized. The oxidized bismuth-based products were demonstrated to undergo reduction with PMe₃, recovering the starting complex 1. Having established a synthetic redox cycle, the catalytic degradation of SF₆ and PhSF₅ was developed through ligand optimization to 5, leading to a 528 TON for SF₆ and the first reported TON for PhSF₅ (3.2).