The reactivity of the hybrid phosphorus-sulfur proligands pr i PSH, phPS 2 H 2 and ePS 2 H 2 with iridium and rhodium precursors has been explored. By reacting IrCl 3 with pr i PSH in the presence of NEt 3 as base, the octahedral Ir(III) specie [Ir(pr i PS) 3 ] was obtained and its crystal structure determined. Reactions of the potentially tridentated proligands phPS 2 H 2 and ePS 2 H 2 with trans-[MF(CO)(PPh 3 ) 2 ] (M=Rh and Ir) were also investigated. Complexes of general formula [M(H)(phPS 2 )(CO)(PPh 3 )] were obtained with phPS 2 H 2 . A single crystal X-ray structure determination for [Rh(H)(phPS 2 )(CO)(PPh 3 )] showed the complex to be octahedral. Reactions with the aliphatic proligand ePS 2 H 2 afforded analogous species to those with phPS 2 H 2 .