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 <i>N</i>,<i>C</i>,<i>N</i> pincer bismuthinidene complexes (<b>1</b> and <b>5</b>). Exposure of SF₆ and PhSF₅ to <b>1</b> 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 <b>1</b>. Having established a synthetic redox cycle, the catalytic degradation of SF₆ and PhSF₅ was developed through ligand optimization to <b>5</b>, leading to a 528 TON for SF₆ and the first reported TON for PhSF₅ (3.2).