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

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posted on 24.09.2002, 00:00 authored by Richard D. Adams, Burjor Captain, Wei Fu, Mark D. Smith
The reaction of Ru5(CO)155-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)45-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.