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Reactions of the trinuclear iron cluster [Fe3Cp2(CO)(3)(mu-CO)(mu(3)-CO)(mu(3)-CF3C2CF3)] (1) with the bis(phosphino) ligands dppm and dppe give different results: dppe yields mainly the hexanuclear compound (2) in which two tri-iron cluster units are linked by the diphosphine, although a trinuclear derivative (3) with a chelating dppe ligand is also obtained as a minor product, whereas dppm displaces carbonyl to give complexes containing exclusively a single tri-iron unit, though the phosphine may be either dangling (4) or chelating (5). The complexes 2-5 have been characterised by elemental analyses and from their IR and NMR spectra, supplemented in the case of 2 by a single crystal X-ray diffraction analysis. (c) 2006 Elsevier B.V. All rights reserved.