Transformation of a μ<sub>3</sub>‑Benzyne Ligand into Phenol on a Cationic Triruthenium Cluster Supported by a μ<sub>3</sub>‑Sulfido Ligand
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A triruthenium complex containing μ3-η2(||)-benzyne and μ3-sulfido ligands, [(Cp*Ru)3(μ3-S){μ3-η2(||)-C6H4}(μ-H)] (2), was synthesized by the reaction of [(Cp*Ru)3(μ3-S)(μ-H)3] (1) with benzene. Although 2 was stable toward oxygen and water, two-electron oxidation of 2 with a Ag(I) salt in the presence of water afforded the dicationic μ-hydroxo complex [(Cp*Ru)3(μ3-S){μ3-η2(||)-C6H4}(μ-OH)]2+ (3). Treatment of 3 with amine resulted in the deprotonation of the μ-hydroxo ligand, and an unsaturated monocationic complex, [(Cp*Ru)3(μ3-S)(μ3-OC6H4-κO,κC)]+ (4), which possesses a μ3-cyclohexadienonediyl ligand, was formed via reductive C–O bond formation between the μ3-benzyne and transient μ-oxo ligands. Phenol was extruded from the Ru3 cluster upon the hydrogenation of 4 via the formation of a μ3-phenoxo complex, [(Cp*Ru)3(μ3-S){μ3-OPh}(μ-H)]+ (5). The cyclic voltammogram of 2 shows two reversible one-electron redox waves, and a dicationic μ3-benzyne complex, [(Cp*Ru)3(μ3-S){μ3-η2:η2(⊥)-C6H4}(μ-H)]2+(8), was shown to be responsible for the uptake of water to yield μ-hydroxo complex 3.
