Faculté des sciences

The water-soluble cluster cation [H3Ru3(C6H6)(C6Me6)2(O)]+: Improved synthesis, aerobic oxidation, electrochemical properties and ligand exchange studies

Vieille-Petit, Ludovic ; Tschan, Mathieu J.-L. ; Süss-Fink, Georg ; Laurenczy, Gabor ; Hagen, Collin M. ; Finke, Richard G. ; Geneste, Florence ; Moinet, Claude

In: Polyhedron, 2005, vol. 24, no. 15, p. 1961-1967

The synthesis of the trinuclear cluster cation [H3Ru3(C6H6)(C6Me6)2(O)]+ (1) has been considerably improved by changes in the NaBH4 addition step and by introducing chromatographic methods; in addition, the redox and ligand exchange properties of 1 have been studied. Although exposure... Plus

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    Summary
    The synthesis of the trinuclear cluster cation [H3Ru3(C6H6)(C6Me6)2(O)]+ (1) has been considerably improved by changes in the NaBH4 addition step and by introducing chromatographic methods; in addition, the redox and ligand exchange properties of 1 have been studied. Although exposure of an aqueous solution of 1 to air yields the oxidised cluster [H3Ru3(C6H6)(C6Me6)2(O) (OH)]+ (2), cyclic voltammetry of [1][BF4] in acetonitrile reveals a first reversible oxidation step that does not involve 2. Bulk electrolysis of 1 and 2 in the same medium affords only decomposition products. Ligand exchange in 1 takes place only at higher temperatures: by heating a mixture of toluene with an aqueous solution of [1][BF4] (1000:1) to 110 °C for 2 h, the formation of the toluene derivative [H3Ru3(C6H5Me)(C6Me6)2 (O)]+ (3) is observed in small quantities. H/D exchange of 1 with D2O does not occur up to 90 °C; however, in the presence of D2, H/D exchange with 1 is observed to give the deuterated derivative [D3Ru3 (C6H6)(C6Me6)2 (O)]+ (1a). The results provide an improved synthesis of 1, as well as information about its redox and ligand-exchange reactions, results necessary to understand and develop the chemistry of 1.