Hydrogenation and Carbon−Sulfur Bond Hydrogenolysis of Benzothiophene Promoted by Re₂(CO)₁₀ and H₄Re₄(CO)₁₂

In the search for metal complexes that promote the cleavage of C−S bonds in thiophenes, we observe that the reaction of Re2(CO)10 and benzothiophene (BT) under a hydrogen atmosphere gives the trinuclear cluster Re3(μ-H)2(μ3-S-2-EtC6H4)(μ-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 Re2(CO)10 initially reacts with H2 to give H3Re3(CO)12, which subsequently converts to H4Re4(CO)12, which finally reacts with BT to give 1.