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The water-soluble cluster cation [H<sub>3</sub>Ru<sub>3</sub>(C<sub>6</sub>H<sub>6</sub>)(C<sub>6</sub>Me<sub>6</sub>)<sub>2</sub>(O)]<sup>+</sup>: Improved synthesis, aerobic oxidation, electrochemical properties and ligand exchange studies
Auteur(s)
Vieille-Petit, Ludovic
Tschan, Mathieu J.-L.
Laurenczy, Gabor
Hagen, Collin M.
Finke, Richard G.
Geneste, Florence
Moinet, Claude
Date de parution
2005
In
Polyhedron, Elsevier, 2005/24/15/1961-1967
Résumé
The synthesis of the trinuclear cluster cation [H<sub>3</sub>Ru<sub>3</sub>(C<sub>6</sub>H<sub>6</sub>)(C<sub>6</sub>Me<sub>6</sub>)<sub>2</sub>(O)]<sup>+</sup> (<b>1</b>) has been considerably improved by changes in the NaBH<sub>4</sub> addition step and by introducing chromatographic methods; in addition, the redox and ligand exchange properties of <b>1</b> have been studied. Although exposure of an aqueous solution of <b>1</b> to air yields the oxidised cluster [H<sub>3</sub>Ru<sub>3</sub>(C<sub>6</sub>H<sub>6</sub>)(C<sub>6</sub>Me<sub>6</sub>)<sub>2</sub>(O) (OH)]<sup>+</sup> (<b>2</b>), cyclic voltammetry of [<b>1</b>][BF<sub>4</sub>] in acetonitrile reveals a first reversible oxidation step that does not involve <b>2</b>. Bulk electrolysis of <b>1</b> and <b>2</b> in the same medium affords only decomposition products. Ligand exchange in <b>1</b> takes place only at higher temperatures: by heating a mixture of toluene with an aqueous solution of [<b>1</b>][BF<sub>4</sub>] (1000:1) to 110 °C for 2 h, the formation of the toluene derivative [H<sub>3</sub>Ru<sub>3</sub>(C<sub>6</sub>H<sub>5</sub>Me)(C<sub>6</sub>Me<sub>6</sub>)<sub>2</sub> (O)]<sup>+</sup> (<b>3</b>) is observed in small quantities. H/D exchange of <b>1</b> with D<sub>2</sub>O does not occur up to 90 °C; however, in the presence of D<sub>2</sub>, H/D exchange with <b>1</b> is observed to give the deuterated derivative [D<sub>3</sub>Ru<sub>3</sub> (C<sub>6</sub>H<sub>6</sub>)(C<sub>6</sub>Me<sub>6</sub>)<sub>2</sub> (O)]<sup>+</sup> (<b>1a</b>). The results provide an improved synthesis of <b>1</b>, as well as information about its redox and ligand-exchange reactions, results necessary to understand and develop the chemistry of <b>1</b>.
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Type de publication
journal article
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