Facile introduction of bridging MPh₂ groups (MGe, 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.