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Nucleophilic addition reactions on the electron-deficient cluster dication [H<sub>4</sub>Ru<sub>4</sub>(C<sub>6</sub>H<sub>6</sub>)<sub>4</sub>]<sup>2+</sup> : synthesis and structural characterisation of the water-soluble cluster cations [H<sub>3</sub>Ru<sub>4</sub>(C<sub>6</sub>H<sub>6</sub>)<sub>4</sub> (CO)]<sup>+</sup> and [H<sub>3</sub>Ru<sub>4</sub>(C<sub>6</sub>H<sub>6</sub>)<sub>4</sub> (OH)]<sup>2</sup>
Auteur(s)
Chérioux, Frédéric
Maisse-François, Aline
Neels, Antonia
Date de parution
2001
In
Journal of the Chemical Society, Dalton Transactions, 2001//2184-2187
Résumé
The electron-deficient (58e) cluster cation [H<sub>4</sub>Ru<sub>4</sub>(C<sub>6</sub>H<sub>6</sub>)<sub>4</sub>]<sup>2+</sup><b>1</b> was found to react in aqueous solution with simple nucleophiles to give electron-precise (60e) clusters. With carbon monoxide, the cluster cation [H<sub>3</sub>Ru<sub>4</sub>(C<sub>6</sub>H<sub>6</sub>)<sub>4</sub>(CO)]<sup>+</sup><b>3</b> is formed. The reaction with water needs NaN<sub>3</sub> as catalyst and yields the cluster dication [H<sub>3</sub>Ru<sub>4</sub>(C<sub>6</sub>H<sub>6</sub>)<sub>4</sub> (OH)]<sup>2+</sup><b>4a</b>; the reaction with alcohols leads to the analogous clusters [H<sub>3</sub>Ru<sub>4</sub>(C<sub>6</sub>H<sub>6</sub>)<sub>4</sub> (OR)]<sup>2+</sup> (R = Me: <b>4b</b>, R = Et: <b>4c</b>, R = PhCH<sub>2</sub>: <b>4d</b>, R = Ph: <b>4e</b>, R = 4-EtC<sub>6</sub>H<sub>4</sub>: <b>4f</b>). The single-crystal X-ray structure analyses of the chloride salts of <b>3</b> and <b>4a</b> reveal a tetrahedral Ru<sub>4</sub> metal core. Each ruthenium atom is coordinated by a η<sup>6</sup>-benzene ligand, while the carbonyl or hydroxo ligands are found as µ<sub>3</sub> capping ligands over a triangular face of the Ru<sub>4</sub> tetrahedron.
Identifiants
Type de publication
journal article
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