Reactivity of C6F5S-P(C6H5)2 with [M3(CO)12] (M = Fe, Ru, Os). The X-ray crystal structures of [Fe2(μ-SC6F5)(μ-PPh2)(CO)6], [Ru4(μ3-SPPh2)2(μ-SC6F5)2(μ-PPh2)2(SC6F5)2(CO)6] and [Os3(η1-Ph2P-SC6F5)(CO)11]

The thiophosphinite C6F5S-P(C6H5)2 (1) was synthesized and its reactivity explored with transition metal clusters of group 8. The reaction of 1 with [M3(CO)12] (M = Fe, Ru, Os) afforded the complexes [Fe2(μ-SC6F5)(μ-PPh2)(CO)6] (2), [Ru4(μ3-SPPh2)2(μ-SC6F5)2(μ-PPh2)2(SC6F5)2(CO)6] (3) and [Os3(η1-Ph2P-SC6F5)(CO)11] (4) in good yields. Complex 2 was the result of the P–S bond activation, while complex 3 resulted from the activation of P–S and C–S bonds. Simple ligand substitution occurs when C6F5S-P(C6H5)2 (1) is reacted with Os3(CO)12.