Iridium–fluorobenzenetiolate complexes of general formula [Ir(SRF)(CO)(PPh3)2], (RF=C6F5 1a, C6HF4-4 1b, C6H4F-4 1c, and C6H4CH3-2 1d), were prepared by methatetical reactions with Tl(SRF) or HSRF. The unexpected trimetallic compound [Ir3(μ-SC6F5)3(μ-CO)(CO)4(PPh3)2] 2 was also isolated when RF=C6F5. Oxidative addition of fluorothiols to the corresponding Ir(I) precursors, afforded the compounds [Ir(H)(Cl)(SRF)(CO)(PPh3)2] (RF=C6F5 3a, C6HF4-4 3b and C6H4F-4 3c) and [Ir(H)(SRF)2(CO)(PPh3)2])] (RF=C6F5 4a, C6HF4-4 4b and C6H4F-4 4c). Irreversible oxygen uptake by compounds 1 gives rise to the oxo-derivatives [Ir(SRF)(O2)(CO)(PPh3)] (RF=C6F5 5a, C6HF4-4 5b, C6H4F-4 5c and C6H4CH3-2 5c). The crystal and molecular structures of [Ir(SC6F5)(CO)(PPh3)2] 1a, [Ir3(μ-SC6F5)3(μ-CO)(CO)4(PPh3)2] 2 and [Ir(SC6F5)(η2-O2)(CO)(PPh3)2] 5a were determined by X-ray diffraction crystallography. Compound 2 contains an asymmetrical Ir3S3 ring with one iridium–iridium bond (2.665(1)Å) doubly bridged by CO and (C6F5S)−.

Financial support from the EU (Contract CI1*-CT930329), DGAPA-IN121698 UNAM and CONACYT (25108E) are gratefully acknowledged.