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  • Publication
    Accès libre
    Supramolecular cluster catalysis : facts and problems
    (2004) ; ;
    Vieille-Petit, Ludovic
    ;
    Tschan, Mathieu J.-L.
    ;
    Romakh, Vladimir B.
    ;
    Ward, Thomas R.
    ;
    Dadras, Massoud
    ;
    Laurenczy, Gabor
    By checking the chemistry underlying the concept of "supramolecular cluster catalysis" we identified two major errors in our publications related to this topic, which are essentially due to contamination problems. (1) The conversion of the "closed" cluster cation [H3Ru3(C6H6)(C6Me6)2(O)]+ (1) into the "open" cluster cation [H2Ru3(C6H6)(C6Me6)2 (O)(OH)]+ (2), which we had ascribed to a reaction with water in the presence of ethylbenzene is simply an oxidation reaction which occurs in the presence of air. (2) The higher catalytic activity observed with ethylbenzene, which we had erroneously attributed to the "open" cluster cation [H2Ru3(C6H6)(C6Me6)2(O)(OH)]+ (2), was due to the formation of RuO2nH2O, caused by a hydroperoxide contamination present in ethylbenzene.
  • Publication
    Accès libre
    Catalytic hydrogenation of aromatics under biphasic conditions: isolation and structural characterisation of the cluster intermediate [(η6-C6Me6)26-C6H6)Ru32-H)2(μ2-OH)(μ3-O)]+
    (2001-03-01)
    Faure, Matthieu
    ;
    Tesouro Vallina, Ana
    ;
    Ludovic Petit
    ;
    ;
    The water-soluble cluster cation [(η6-C6Me6)26-C6H6)Ru32-H)33-O)]+ (2) catalyses the hydrogenation of benzene and benzene derivatives to give the corresponding cyclohexanes under biphasic conditions. The catalytic activity of 2 depends markedly on the substrate, an extremely high activity being observed for ethylbenzene. The cationic species present in the catalytic mixture of the ethylbenzene hydrogenation could be isolated as the tetrafluoroborate salt and characterised as the cation [(η6-C6Me6)26-C6H6)Ru32-H)22-OH)(μ3-O)]+ (3). With 3 as the catalyst, the catalytic activity is also much higher for other benzene derivatives.