Various new thio-and selenosulfonato complexes of iron were synthesized by straight forward route. Treatment of the iron chalcogenides, (mu-E-x)[CpFe(CO)(2)](2) (E = S; x = 2-4, E = Se; x = 1) with sulfonyl chlorides produced the corresponding thio-or selenosulfonato complexes CpFe(CO)(2)ESO2Ar [Ar = 2-C4H3S (1), 5-C4H2SCl (2), 1,3-C6H4SO2Cl (3), 1,3-C6H4CO2H (4); E = S (a), Se (b)]. The dimers [CpFe(CO)(2) ESO2](2)(1,3-C6H4) (5) are obtained from the iron chalcogenides with 1,3-C6H4(SO2Cl) 2 in a 2:1 molar ratio. All of these new complexes have been characterized by IR, H-1, C-13 NMR spectroscopy, UV-Vis and elemental analysis. The X-ray structure of CpFe(CO)(2)ESO2-1,3-C6H4SO2Cl (3a) is determined. (C) 2014 Elsevier B.V. All rights reserved.