In the search for metal complexes that promote the cleavage of C-S bonds in thiophenes, we observe that the reaction of Re-2-(CO)(10) and benzothiophene (BT) under a hydrogen atmosphere gives the trinuclear cluster Re-3(mu-H)(2)(mu(3)-S-2-EtC6H4)(mu-2,3-DHBT)(CO)(9) (1), which contains a hydrogenated BT ligand and a thiolate ligand resulting from the hydrogenation and cleavage of a C-S bond in BT. A detailed study of the reaction shows that Re-2(CO)(10) initially reacts with H-2 to give H3Re3(CO)(12), which subsequently converts to H4Re4(CO)(12), which finally reacts with BT to give 1.