Reactivity of Fe3(CO)12 towards thiols containing an α,β-unsaturated ketone system

The unsaturated derivatives [Fe2(CO)6(μ-S2CCHC(O)C6H4X)] (X=F, OMe) have been isolated by reaction of [(HS)2CCHC(O)C6H4X] (X=F, OMe) with Fe3(CO)12 in dried THF. Addition of Fe2(CO)9 to a solution of [Fe2(CO)6(μ-S2CCHC(O)C6H4OMe)] affords [Fe(CO)4{μ-(OMe)C6H4C(O)CHC(S)2Fe2(CO)6}]. The new compounds have been characterised by analytical and spectroscopic data and the crystal structure of [Fe2(CO)6(μ-S2CCHC(O)C6H4F)] has been solved by X-ray diffraction.