Reaction of Fe-3(mu(3)-S)(2)(CO)(9) (A) with 1,2-bis(diphenylphosphino)ethane (Ph2PCH2CH2PPh2, dppe) in the presence of the decarbonylating agent Me3NO center dot 2H(2)O in MeCN at room temperature afforded [Fe-3(mu(3)-S)(2)(CO)(8)](2)(Ph2PCH2CH2PPh2) (1) containing bridging diphosphine ligand in 50% yield. The title complex 1 was structurally characterized by IR and NMR spectroscopic analysis. In addition, the molecular structure of 1 was further determined by X-ray crystallography. The molecule is centrosymmetric and the phosphorus atoms of DPPE reside in a basal position of the square-pyramidal geometry of the iron atoms.