Synthesis of neutral iridium(III) and rhodium(III) complexes with the proligands Pri2P(C6H4SH-2) [priPSH]; PhP(C6H4SH-2)2 [phPS2H2] and PhP(C2H4SH)2 [ePS2H2]. The X-ray crystal structures of [Ir(priPS)3] and [Rh(H)(phPS2)(CO)(PPh3)]

The reactivity of the hybrid phosphorus–sulfur proligands priPSH, phPS2H2 and ePS2H2 with iridium and rhodium precursors has been explored. By reacting IrCl3 with priPSH in the presence of NEt3 as base, the octahedral Ir(III) specie [Ir(priPS)3] was obtained and its crystal structure determined. Reactions of the potentially tridentated proligands phPS2H2 and ePS2H2 with trans-[MF(CO)(PPh3)2] (M=Rh and Ir) were also investigated. Complexes of general formula [M(H)(phPS2)(CO)(PPh3)] were obtained with phPS2H2. A single crystal X-ray structure determination for [Rh(H)(phPS2)(CO)(PPh3)] showed the complex to be octahedral. Reactions with the aliphatic proligand ePS2H2 afforded analogous species to those with phPS2H2.