Facile introduction of bridging MPh2 groups (MGe, Sn, Pb) into platinum–pentaruthenium and hexaruthenium carbido carbonyl cluster complexes

The reactions of PtRu5(CO)16(μ6-C) (1) with Ph3GeH and Ph3SnH afforded the trimetallic cluster complexes PtRu5(CO)15(μ-GePh2)(μ6-C) (4) and PtRu5(CO)15(μ-SnPh2)(μ6-C) (5), respectively, in good yields. Both the compounds consist of an octahedral cluster of one platinum and five ruthenium atoms with an interstitial carbido ligand in the center. The bridging CO ligand in 1 was replaced by a bridging GePh2 group in 4 and a bridging SnPh2 group in 5. The lead homologue PtRu5(CO)15(μ-PbPh2)(μ6-C) (6) was obtained from the reaction of 1 with Pb2Ph6. The reaction of PtRu5(CO)15(PMe2Ph)(μ6-C) (2) with Ph3SnH yielded the phosphine derivative of 5, PtRu5(CO)14(μ-SnPh2)(PMe2Ph)(μ6-C) (7). Compound 7 was obtained in a higher yield from the reaction of 5 with PMe2Ph. The reaction of Ru6(CO)14(η6-C6H6)(μ6-C) (3) with Ph3SnH yielded the new hexaruthenium complex Ru6(CO)13(μ-SnPh2)(η6-C6H6)(μ6-C) (8) containing a bridging SnPh2 ligand. Evidence for benzene formation in the formation of compound 5 indicates the fate of the phenyl group that was cleaved from the tin atom in that reaction.