The readily prepared [Re 2 (CO) 6 (μ-S 2 NC 7 H 4 ) 2 ] (1) reacts with Group 8 trimetallic carbonyl clusters to yield new mixed-metal tri- and tetranuclear clusters. With [Os 3 (CO) 10 (NCMe) 2 ] at 80°C the tetranuclear mixed-metal cluster [Os 3 Re(CO) 13 (μ 3 -C 7 H 4 NS 2 )] (2) is the only isolated product. With Ru 3 (CO) 12 products are dependent upon the reaction temperature. At 80°C, a mixture of tetranuclear mixed-metal [Ru 3 Re(CO) 13 (μ 3 -C 7 H 4 NS 2 )] (5) and the triruthenium complex [Ru 3 (CO) 9 (μ-H)(μ 3 -C 7 H 4 NS 2 )] (4) results, while at 110°C a second tetranuclear mixed-metal cluster, [Re 2 Ru 2 (CO) 12 (μ 4 -S)(μ-C 7 H 4 NS)(μ-C 7 H 4 NS 2 )] (3), resulting from carbon–sulfur bond scission, is the major product. Reaction of 1 With Fe 3 (CO) 12 at 80°C furnishes the trinuclear mixed-metal cluster [Fe 2 Re(CO) 8 (μ-CO) 2 (μ 3 -C 7 H 4 NS 2 )] (6). The reactivity of 6 has been probed with the aim of identifying any metal-based selectivity for carbonyl substitution. Addition of PPh 3 in presence of Me 3 NO at 25°C gives both the mono- and bis(phosphine)-substituted derivatives [Os 3 Re(CO) 12 (PPh 3 )(μ 3 -C 7 H 4 NS 2 )] (7) and [Os 3 Re(CO) 11 (PPh 3 ) 2 (μ 3 -C 7 H 4 NS 2 )] (8). In 7 the PPh 3 ligand occupies an axial site on wingtip osmium, while in 8 one PPh 3 ligand is equatorially coordinated to wingtip osmium and the other is bonded to a hinge osmium. New complexes have been characterized by a combination of spectroscopic data and single crystal X-ray diffraction studies.