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The salts of [(μ -RE)(μ-CO)Fe2(CO)6] -[Et3NH]+(E = S. Se, Te) react withbenzenesulfinyl chloride to give the μ -sulfinyl group bridged complexes (μ-RE)(μ- PhS=O)Fe2(CO6), in good yields. Whereas the salts [(μ -RS)(μ -CO)Fe2(CO)6]-[Et_3NH]+(R =t- Bu, Ph) react with carbon disulfide to yield the dithioformato-bridged anionic salts [(μ -RS)(μ- S=C-S)Fe2(CO)6]-[Et3NH], which react in situ at the exo-sulfur atom of the dithioformato-groupwith diverse α.β-unsaturated carbonyl compounds to give Michael addition products inmoderate yields.