Abstract The enzyme thioredoxin reductase (TrxR) is attracting much interest as a potential target for cancer therapy. The presence of a selenium atom in the catalytic site makes it sensitive to inhibition by electrophilic molecules, including the Au I complex auranofin [2, 3, 4, 6-tetra-O-acetyl-1-thio-β-D-glucopyranosato-S-(triethylphosphane) gold]. The reactions between auranofin and models of thiol and selenol nucleophiles present in TrxR (PhSH ...