The first heterometallic clusters containing the SnR′₂(R′= 2,4,6-triisopropylphenyl) moiety have been prepared. Triruthenium dodecacarbonyl reacted at low temperatures with SnR′₂ or, at higher temperatures, with its trimer (SnR′₂)₃ to give both [Ru₃(CO)₁₀(µ-SnR′₂)₂]1 and [Ru₃(CO)₉(µ-SnR′₂)₃]2. Reaction of the pentametallic species [Ru₃(CO)₁₀(µ-SnL₂)₂][L = R = CH(SiMe₃)₂3 or R′] with SnR′₂ or SnR₂ respectively afforded the hexametallic clusters [Ru₃(CO)₉(µ-SnR₂)(µ-SnR′₂)₂]4 and [Ru₃(CO)₉(µ-SnR₂)₂(µ-SnR′₂)]5. In the reaction of [Ru₃(CO)₁₂] with SnR₂ the hexametallic cluster [Ru₃(CO)₉(µ-SnR₂)₃]6 has now been isolated in addition to the previously reported Ru₃Sn₂ cluster. The trimer (SnR′₂)₃ also reacted with [Ru₃(CO)₁₀(dppm)](dppm = Ph₂PCH₂PPh₂) to give [Ru₃(CO)₈(µ-SnR′₂)₂(dppm)]7, whereas with SnR₂ the product was [Ru₂(CO)₆(µ-SnR₂)(µ-dppm)]8. Compound 7 can also be obtained by the reaction of 2 with dppm, using sodium–benzophenone to activate the cluster. Reaction of the dodecacarbonyl with Sn[CH(PPh₂)₂]₂ or its lead analogue surprisingly did not yield a mixed cluster, but afforded a rapid and quantitative route to [Ru₃(CO)₁₀(dppm)]. Compound 2 behaves similarly, yielding 7 again in high yield. The crystal and molecular structures of 2, 4, 5 and 8 have been determined. In compounds 2, 4 and 5, the ruthenium triangle and the three tin atoms form a planar array. A detailed comparison of ligand steric effects is made. In 8 the metal atoms and the two P atoms are coplanar, with a long Ru–Ru vector bridged by the R₂Sn group and the diphosphine [2.954(2)Å]. The structure of 4 is unusual, the characteristic aryltin twist on only two of the three tin atoms generating chirality, resulting in a spiral packing in space group P6₅. This structure was determined both diffractometrically and using two different image-plate systems, and the results are remarkably consistent in all three cases.