Faculté des sciences

Chiral Arene Ruthenium Complexes : Synthesis and Molecular Structure of the Enantiopure Cluster Cation (S)-[H3Ru3{C6H5[CH(CH3)CH2OH]}(C6Me6)2(O)]+

Vieille-Petit, Ludovic ; Therrien, Bruno ; Süss-Fink, Georg

In: European Journal of Inorganic Chemistry, 2003, vol. 5, p. 3707 - 3711

The reaction of enantiopure (R)-(2-cyclohexa-1,4-dienyl)propan-1-ol with ruthenium chloride hydrate yields, without racemisation of the chiral ligand, the chloro-bridged dinuclear complex (S,S)-[RuCl2{C6H5[CH(CH3)CH2OH]}]2 (1). The dimer 1 reacts with triphenylphosphane to give the mononuclear complex... Plus

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    Summary
    The reaction of enantiopure (R)-(2-cyclohexa-1,4-dienyl)propan-1-ol with ruthenium chloride hydrate yields, without racemisation of the chiral ligand, the chloro-bridged dinuclear complex (S,S)-[RuCl2{C6H5[CH(CH3)CH2OH]}]2 (1). The dimer 1 reacts with triphenylphosphane to give the mononuclear complex (S)-[RuCl2{C6H5[CH(CH3)CH2OH]}(PPh3)] (2). A single-crystal X-ray structure analysis of 2 reveals the absolute configuration of the asymmetric carbon atom to have remained, the change from (R) to (S) 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 (S)-[Ru{C6H5[CH(CH3)CH2OH]}(H2O)3]2+, formed in situ from 1 in aqueous solution, reacts with the dinuclear complex [H3Ru2(C6Me6)2]+ to give a chiral trinuclear arene-ruthenium cluster, the cation (S)-[H3Ru3{C6H5[CH(CH3)CH2OH]} (C6Me6)2(O)]+ (3). This enantiopure cation has been isolated and characterised as its tetrafluoroborate salt. The single-crystal X-ray structure analysis of (S)-[3][BF4] shows a strong intramolecular hydrogen bond between the μ3-oxo cap and the hydroxy function, which also persists in acetone solvent, as demonstrated by NMR spectroscopy.