Ir(CO)[CpFe{eta5-C5H3(PPh2)CH2SR}]Cl [R = Ph and (t)Bu], containing a kappa2:P,S ligand, undergoes H2 addition across the S-Ir-CO axis under kinetic control to form two distinct diastereoisomeric products, which then rearrange via S dissociation in a process that can be hijacked for useful catalysis, but ultimately form a single diastereoisomer of the thermodynamic product where the hydride ligands are trans to chloride and phosphine.