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Therrien, Bruno
Nom
Therrien, Bruno
Affiliation principale
Fonction
Professeur titulaire
Email
bruno.therrien@unine.ch
Identifiants
Résultat de la recherche
Voici les éléments 1 - 3 sur 3
- PublicationAccès libreSynthesis of a trinuclear cation [H3Ru3(Fc-arene)(C6Me6)2(O)]+ containing a ferrocenyl group tethered to an arene ligand(2003-11-20)
; Ferrocene carboxylic acid 2-cyclohexa-1,4-dienyl-ethyl ester (1) is prepared from ferrocene carboxylic acid and 2-cyclohexa-1,4-dienyl-ethanol. This diene reacts with RuCl3•nH2O in refluxing ethanol to afford quantitatively [Ru(Fc-arene)Cl2]2 (2) (Fc-arene=ferrocene carboxylic acid phenethyl ester). The dinuclear complex 2 reacts with triphenylphosphine to give the mononuclear complex [Ru(Fc-arene)(PPh3)Cl2] (3). The trinuclear arene-ruthenium cluster cation [H3Ru3 (Fc-arene)(C6Me6)2(O)]+ (4) is synthesised from the dinuclear precursor [H3Ru2 (C6Me6)2]+ and the mononuclear complex [Ru(Fc-arene)(H2O)3]2+, accessible from 2 in aqueous solution. The water-soluble trinuclear cluster cation 4 catalyses the hydrogenation of benzene to give cyclohexane under biphasic conditions. - PublicationAccès libreSynthesis and molecular structure of the trinuclear ruthenium cluster cations [H3Ru3(C6H6)(C6H2Me4)2(O)]+ and [H3Ru3{C6H5(CH2)2OH}(C6H2Me4)2(O)]+(2003-11-20)
; The trinuclear arene–ruthenium cluster cations [H3Ru3(C6H6)(C6H2Me4)2(O)]+ (2) and [H3Ru3{C6H5(CH2)2OH}(C6H2Me4)2(O)]+ (3) have been synthesised from the dinuclear precursor [H3Ru2(C6H2Me4)2]+ (1) and the mononuclear complexes [Ru(C6H6)(H2O)3]2+ and [Ru{C6H5(CH2)2OH}(H2O)3]2+, isolated and characterised as the tetrafluoroborate salts. Cations 2 and 3 are analogues of the cluster cation [H3Ru3(C6H6)(C6Me6)2(O)]+ which was found to catalyse the hydrogenation of benzene to give cyclohexane under biphasic conditions (‘supramolecular cluster catalysis’). The single-crystal X-ray structure analyses of 2 and 3 have been determined. Unlike [2][BF4]•3H2O, [3][PF6]•H2O shows a dimeric structure in the solid state, thanks to hydrogen bonds between the hydroxo function of one molecule of 3, a water molecule and the oxo cap of an other molecule of 3. - PublicationAccès libreIsolation and single-crystal X-ray structure analysis of the catalyst–substrate host–guest complexes [C6H6⊂H3Ru3{C6H5(CH2) nOH}(C6Me6)2(O)]+ (n = 2, 3)(2003-11-01)
; ; Ward, Thomas R.The trinuclear arene-ruthenium cluster cations [H3Ru3{C6H5 (CH2)nOH}(C6Me6)2 (O)]+ (3: n=2, 4: n=3) have been synthesised from the dinuclear precursor [H3Ru2 (C6Me6)2]+ and the mononuclear complexes [{C6H5(CH2)nOH}Ru(H2O)3]2+ in aqueous solution, isolated and characterised as the hexafluorophosphate or tetrafluoroborate salts. Both 3 and 4 are derivatives of the parent cluster cation [H3Ru3 (C6H6)(C6Me6)2(O)]+ (1) which was found to catalyse the hydrogenation of benzene to give cyclohexane under biphasic conditions. The mechanism postulated for this catalytic reaction (‘supramolecular cluster catalysis’), involving the hydrophobic pocket spanned by the three arene ligands in 1, was based on the assumption that the substrate molecule benzene is hosted inside the hydrophobic pocket of the cluster molecule to form a catalyst–substrate host–guest complex in which the hydrogenation of the substrate takes place. With the analogous cluster cations 3 and 4, containing a (CH2)nOH side-arm (n=2, 3) as substituent at the benzene ligand, it was possible to isolate the cationic host–guest complexes as the hexafluorophosphate or tetrafluoroborate salts. The single-crystal X-ray structure analyses of [C6H6⊂3][PF6] and [C6H6⊂4][BF4], compared to that of [3][PF6] show that the substrate molecule benzene is indeed held inside the hydrophobic pocket of 3 and 4, the angle between the metal (Ru3) plane and the aromatic plane being 67° and 89°, respectively.