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STRUCTURAL CHARACTERISATION OF HYDROXO-BRIDGED ARENE-RUTHENIUM AND -OSMIUM COMPLEXES: FURTHER REACTIONS OF HYDROXO-BRIDGED COMPLEXES

Reaction of <2> with an excess of either aqueous NaOH or Na2CO3 followed by addition of Na gave two products, previously formulated as BPh4 (II) and <(eta-C6H6)M(OH)3M(eta-C6H6)>BPh4*Me2CO (M = Ru (III), Os (IV)).X-ray structural analyses now reveal that the latter should be reformulated as the novel (BPh4)2*2Me2CO tetramers containing a tetrahedrally coordinated O2- ion.In contrast, with substituted arenes the binuclear triple hydroxo-bridged cations of type III are formed asevidenced by the X-ray crystal structure determination of Cl*3H2O (V).Reactions of these various hydroxo-bridged complexes with HX (X = Cl, Br, I) gives either + and/or <2> whereas with CF3CO2H in the presence of arene’, the dications 2+ are formed.

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Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI