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Chiral Arene Ruthenium Complexes : Synthesis and Molecular Structure of the Enantiopure Cluster Cation (<i>S</i>)-[H<sub>3</sub>Ru<sub>3</sub>{C<sub>6</sub>H<sub>5</sub>[CH(CH<sub>3</sub>)CH<sub>2</sub>OH]}(C<sub>6</sub>Me<sub>6</sub>)<sub>2</sub>(O)]<sup>+</sup>
Auteur(s)
Date de parution
2003
In
European Journal of Inorganic Chemistry, 2003/5/3707 - 3711
Résumé
The reaction of enantiopure (<i>R</i>)-(2-cyclohexa-1,4-dienyl)propan-1-ol with ruthenium chloride hydrate yields, without racemisation of the chiral ligand, the chloro-bridged dinuclear complex (<i>S,S</i>)-[RuCl<sub>2</sub>{C<sub>6</sub>H<sub>5</sub>[CH(CH<sub>3</sub>)CH<sub>2</sub>OH]}]<sub>2</sub> (<b>1</b>). The dimer <b>1</b> reacts with triphenylphosphane to give the mononuclear complex (<i>S</i>)-[RuCl<sub>2</sub>{C<sub>6</sub>H<sub>5</sub>[CH(CH<sub>3</sub>)CH<sub>2</sub>OH]}(PPh<sub>3</sub>)] (<b>2</b>). A single-crystal X-ray structure analysis of <b>2</b> reveals the absolute configuration of the asymmetric carbon atom to have remained, the change from (<i>R</i>) to (<i>S</i>) being due to the priority change caused by coordination; in the solid state, onedimensional hydrogen-bonded chains are formed between the hydroxy functions and chloro ligands of neighbouring molecules. The mononuclear cationic complex (<i>S</i>)-[Ru{C<sub>6</sub>H<sub>5</sub>[CH(CH<sub>3</sub>)CH<sub>2</sub>OH]}(H<sub>2</sub>O)<sub>3</sub>]<sup>2+</sup>, formed in situ from <b>1</b> in aqueous solution, reacts with the dinuclear complex [H<sub>3</sub>Ru<sub>2</sub>(C<sub>6</sub>Me<sub>6</sub>)<sub>2</sub>]<sup>+</sup> to give a chiral trinuclear arene-ruthenium cluster, the cation (<i>S</i>)-[H<sub>3</sub>Ru<sub>3</sub>{C<sub>6</sub>H<sub>5</sub>[CH(CH<sub>3</sub>)CH<sub>2</sub>OH]} (C<sub>6</sub>Me<sub>6</sub>)<sub>2</sub>(O)]<sup>+</sup> (<b>3</b>). This enantiopure cation has been isolated and characterised as its tetrafluoroborate salt. The single-crystal X-ray structure analysis of (<i>S</i>)<sup>-</sup>[<b>3</b>][BF<sub>4</sub>] shows a strong intramolecular hydrogen bond between the μ<sub>3</sub>-oxo cap and the hydroxy function, which also persists in acetone solvent, as demonstrated by NMR spectroscopy.
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Type de publication
journal article
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