Face-coordinated C₆₀ complexes with carbido pentaruthenium cluster cores including a bimetallic platinum-pentaruthenium complex

Interaction of Ru₅C(CO)₁₅ with C₆₀ in refluxing chlorobenzene followed by PPh₃ or dppe (1,2-bis(diphenylphosphino)ethane) forms Ru₅C(CO)₁₁(PPh₃)(μ₃-η ²,η²,η²-C₆₀) (1) or Ru₅C(CO)₁₀-(μ-η¹,η ¹-dppe)(μ₃-η²,η ²,η²-C₆₀) (2), isolated in 19% and 14% yields, respectively, after chromatography. An analogous reaction of Ru₅C(CO)₁₅ with C₆₀ followed by dppf (1,1′-bis(diphenylphosphino)ferrocene) initially forms both Ru₅C(CO)₁₁(η¹-dppf)(μ ₃-η²,η²,η²-C ₆₀) (3) and Ru₅C(CO)₁₀(μ-η¹,η ¹-dppf)(μ₃-η²,η ²,η²-C₆₀) (4), but further thermolysis of 3 in refluxing chlorobenzene converts it to 4. Direct interaction of Ru₅C(CO)₁₄(PPh₃) (5), Ru₅C(CO)₁₃(dppe) (6), and Ru₅C(CO)₁₃(dppf) (7) with C₆₀ in refluxing chlorobenzene also provides 1, 2, and 4 in isolated yields of 21%, 27%, and 20%, respectively. Interaction of PtRu₅C(CO)₁₆ or PtRu₅C-(CO)₁₄(COD) with C₆₀ followed by dppe in refluxing chlorobenzene forms PtRu₅C(CO)₁₁(η²-dppe)(μ ₃-η²,η²nη²-C ₆₀) (8) (7% and 23% yields, respectively). Substitution of the COD ligand in PtRu₅C(CO)₁₄(COD) by dppe at room temperature provides PtRu₅C(CO)₁₄(η²-dppe) (9). Compound 9 does not react with C₆₀ to give 8. All new compounds have been characterized by a combination of analytical and spectroscopic methods, and the molecular structures of compounds 1, 2, 4, 7, 8, and 9 have been determined by single-crystal X-ray diffraction studies.