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

Article abstract of DOI:10.1016/0022-328X(84)85081-0

Reaction of <2> with an excess of either aqueous NaOH or Na2CO3 followed by addition of Na gave two products, previously formulated as <η-C6H6(OH)M(OH)2M(H2O)(η-C6H6)>BPh4 (II) and <(η-C6H6)M(OH)3M(η-C6H6)>BPh4*Me2CO (M = Ru (III), Os (IV)).X-ray structural analyses now reveal that the latter should be reformulated as the novel 2-OH)4(μ₄-O)>(BPh4)2*2Me2CO tetramers containing a tetrahedrally coordinated O^2- 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.