High Nuclearity Ruthenium−Tin Clusters from the Reactions of Triphenylstannane with Pentaruthenium Carbonyl Carbido Cluster Complexes

The reaction of Ru₅(CO)₁₅(μ₅-C), 1, with Ph₃SnH in the presence of UV irradiation has yielded the Ph₃SnH adduct Ru₅(CO)₁₅(SnPh₃)(μ₅-C)(μ-H), 3, by SnH bond activation and cleavage of one Ru−Ru bond in the cluster of 1. The reaction of 1 with Ph₃SnH at 127 °C yielded the high nuclearity cluster compound Ru₅(CO)₁₀(SnPh₃)(μ-SnPh₂)₄(μ₅-C)(μ-H), 4, that contains five tin ligands. Four of these are SnPh₂ groups that bridge each edge of the base of the Ru₅ square pyramidal cluster. The reaction of Ph₃SnH with the benzene-substituted cluster Ru₅(CO)₁₂(C₆H₆)(μ₅-C), 2, at 68 °C yielded two products:  Ru₅(CO)₁₁(SnPh₃)(C₆H₆)(μ₅-C)(μ-H), 5, and Ru₅(CO)₁₀(SnPh₃)₂(C₆H₆)(μ₅-C)(μ-H)₂, 6. Both contain square pyramidal Ru₅ clusters with one and two SnPh₃ groups, respectively. At 127 °C, the reaction of 2 with an excess of Ph₃SnH has led to the formation of two new high-nuclearity cluster complexes:  Ru₅(CO)₈(μ-SnPh₂)₄(C₆H₆)(μ₅-C), 7, and Ru₅(CO)₇(μ-SnPh₂)₄(SnPh₃)(C₆H₆)(μ₅-C)(μ-H), 8. Both compounds contain square pyramidal Ru₅ clusters with SnPh₂ groups bridging each edge of the square base. Compound 8 contains a SnPh₃ group analogous to that of compound 4. When treated with CO, compound 8 is converted to 4. When heated to 68 °C, compound 5 was converted to the new compound Ru₅(CO)₁₁(C₆H₆)(μ₄-SnPh)(μ₃-CPh), 9, by loss of benzene and the shift of a phenyl group from the tin ligand to the carbido carbon atom to form a triply bridging benzylidyne ligand and a novel quadruply bridging stannylyne ligand.