The reactions of the basal edge-bridged square pyramidal hexanuclear cluster [Ru6(μ3-H)2(μ5-κ2-ampy)(μ-CO)2(CO)14] (1; H2ampy = 2-amino-6-methylpyridine) with arenes at high temperature (>110 °C) give [Ru6(μ3-H)2(μ5-κ2-ampy)(η6-arene)(μ-CO)2(CO)11] (arene = C6H6 2a, C6H5Me 2b, 1,4-C6H4Me2 2c). These complexes result from the substitution of the arene for the three CO ligands of the apical Ru atom of 1. Cycloheptatriene reacts with complex 1 in chlorobenzene at reflux temperature to give a mixture of products from which the hexanuclear cluster complexes [Ru6(μ3-H)(μ5-κ2-ampy)(η5-C7H9)(μ3-CO)(μ-CO)2(CO)11] (3), [Ru6(μ3-H)(μ5-κ2-ampy)(μ3-η7-C7H7)(μ-CO)2(CO)11] (4), [Ru6(μ5-κ2-ampy)(μ2-η7-C7H7)2(μ-CO)(CO)9] (5), and [Ru6(μ6-C)(μ3-η7-C7H7)2(μ-CO)2(CO)8] (6) have been isolated and characterized. While compound 3 has a terminal η5-cycloheptadienyl ligand, 4 contains a face-capping η5:η2-cycloheptatrienyl ligand, and 5 has two edge-bridging η4:η3-cycloheptatrienyl ligands. Compound 6, a minor product of this reac...