Synthesis and characterization of bridged and chelated diphosphine coordinated transition metal chalcogenide clusters, [(CO)18Fe6(μ3-Te)4{μ-PPh2(CH2)2PPh2}] and [(CO)nFe2(μ3-Y)2M{PPh2-R-PPh2}], [Y = Se, Te; M = Pd, Fe; n = 6, 8; R = {(η5-C5H4)2Fe}, {(CH2)

Ferrocenyl diphosphine containing iron–palladium clusters [(CO)6Fe2(μ3-Y)2Pd{PPh2(η5-C5H4)Fe(η5-C5H4)PPh2})] (Y = Se (9); Y = Te (10)) have been prepared by the room temperature reaction of [(CO)6Fe2(μ3-Y)2Pd(PPh3)2] (Y = Se(5), Te(6)) with dppf. Structural characterization reveals an unusual chelating coordination by ferrocenyl diphosphine ligand attached to palladium atom. Room temperature reactions of dppe with metal clusters [Fe3(μ3-Te)2(CO)9] (1), [Fe3(μ3-Te)2(CO)8PPh3] (2) and [(CO)6Fe2(μ3-Y)2Pd(PPh3)2] (Y = Se(5), Te(6)) have been performed to obtain chalcogenide metal clusters [(CO)18Fe6(μ3-Te)4{μ-PPh2(CH2)2PPh2}] (3), [Fe3(μ3-Te)2(CO)8{PPh2(CH2)2PPh2}] (4) and [(CO)6Fe2(μ3-Y)2Pd{PPh2(CH2)2PPh2}] (Y = Se (7); Y = Te (8)) respectively. In all the compounds the diphosphine ligands are attached to metal centres by forming either chelating or bridging mode. The structures of compounds 3, 4, 7 and 9 have been established by single crystal X-ray crystallography.