The reactive anionic salts [Et 3 NH][(μ-RE)(μ-CO)Fe 2 (CO) 6 ] (1) (RE=PhS, PhSe) reacted with N-arylbenzimidoyl chloride Ph(Cl)C NAr' (2) (Ar=Ph, 4-MeC 6 H 4 , 4-C 6 H 4 ) in THF to give butterfly σ,μ-iminoacyl bridged hexacarbonyldiiron clusters (μ-RE)(σ,μ-PhC NAr')Fe 2 (CO) 6 (3a-e) in moderate yields. The structure of the new clusters was characterized by elemental analyses, IR and 1 H-NMR spectroscopy. X-ray diffraction confirmed the crystal structure of (μ-PhSe)(σ,μ-PhC NPh)Fe 2 (CO) 6 (3a). It crystallizes in the triclinic space group P1 (no. 2) with a=11.224(3), b=13.542(4), c=8.9559(2) 9, α=102.32(2), β=91.95(2), γ=70.20(2) o , V=1250.1(6) 9 3 , Z=2 and D c a l c =1.636 g cm - 3 .