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Therrien, Bruno

Nom
Therrien, Bruno
Affiliation principale
Fonction
Professeur titulaire
Email
bruno.therrien@unine.ch
Identifiants
https://libra.unine.ch/handle/123456789/382
_
0000-0002-0388-2745

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  • Publication
    Accès libre
    Hydrogen-bonded systems between monocarboxylic acids and the trinuclear cluster cation [H3Ru3(C6H6)(C6Me6)2(O)]+ : cold-spray ionisation mass spectroscopic and X-ray crystallographic studies
    (2004-09-01)
    Therrien, Bruno 
    ;
    Vieille-Petit, Ludovic
    ;
    Süss-Fink, Georg 
    ;
    Sei, Yoshihisa
    ;
    Yamaguchi, Kentaro
    The hydrogen-bonded systems formed between monocarboxylic acid derivatives and the trinuclear arene-ruthenium cluster cation [H3Ru3(C6H6)(C6Me6)2(O)]+ (1) have been studied in solution by cold-spray ionisation mass spectroscopy (CSI-MS) and in the solid state by single-crystal X-ray structure analysis of the tetrafluoroborate salts. The presence of 1:1 (acid:cluster) adducts in acetone solution has been clearly demonstrated by CSI-MS. Single-crystal X-ray structure analyses of selected acid-cluster complexes show that in every case the hydroxyl of the acid function interacts strongly with the μ3-oxo ligand of cation 1, the O … O distance ranging from 2.499(9) to 2.595(11) Å.
  • Publication
    Accès libre
    Ruthenium(II) complexes with ferrocene-modified arene ligands: synthesis and electrochemistry
    (2004)
    Therrien, Bruno 
    ;
    Vieille-Petit, Ludovic
    ;
    Jeanneret-Gris, Julie
    ;
    Štěpnička, Petr
    ;
    Süss-Fink, Georg 
    A series of arene–ruthenium complexes of the general formula [RuCl2{η6-C6H5 (CH2)2R}L] with R=OH, CH2OH, OC(O)Fc, CH2OC(O)Fc (Fc=ferrocenyl) and L=PPh3, (diphenylphosphino)ferrocene, or bridging 1,1′-bis(diphenylphosphino)ferrocene, have been synthesized. Two synthetic pathways have been used for these ferrocene-modified arene–ruthenium complexes: (a) esterification of ferrocene carboxylic acid with 2-(cyclohexa-1,4-dienyl)ethanol, followed by condensation with RuCl3 • nH2O to afford [RuCl2{η6-C6H5 (CH2)2OC(O)Fc}]2, and (b) esterification between ferrocene carboxylic acid and [RuCl2{η6-C6H5 (CH2)3OH}L] to give [RuCl2{η6-C6H5 (CH2)3OC(O)Fc}L]. All new compounds have been characterized by NMR and IR spectroscopy as well as by mass spectrometry. The single-crystal X-ray structure analysis of [RuCl2{η6-C6H5 (CH2)3OH}(PPh3)] shows that the presence of a CH2CH2CH2OH side-arm allows [RuCl2{η6-C6H5 (CH2)3OH}(PPh3)] to form an intramolecular hydrogen bond with a chlorine atom. The electrochemical behavior of selected representative compounds has been studied. Complexes with ferrocenylated side arms display the expected cyclic voltammograms, two independent reversible one-electron waves of the Ru(II)/Ru(III) and Fe(II)/Fe(III) redox couples. Introduction of a ferrocenylphosphine onto the ruthenium is reflected by an additonal reversible, one-electron wave due to ferrocene/ferrocenium system which is, however, coupled with the Ru(II)/Ru(III) redox system.
  • Publication
    Accès libre
    An asymmetric trihydrido-bridged arene ruthenium complex
    (2004)
    Vieille-Petit, Ludovic
    ;
    Therrien, Bruno 
    ;
    Süss-Fink, Georg 
    Reaction of [Ru(η6-indane)(H2O)3]2+ and [Ru(η6-C6Me6)(H2O)3]2+ with NaBH4 in water gives a mixture of three triple hydrido-bridged arene ruthenium cations [(η6-arene)Ru(μ-H)3Ru(η6-arene′)]+ (arene=indane and hexamethylbenzene; arene′=indane and hexamethylbenzene). After treatment with NaBF4, the three complexes are separated by column chromatography and the asymmetrical [(η6-indane)Ru(μ-H)3Ru(η6-C6Me6)][BF4] (cation 1a) can be isolated in moderate yield. 1a decomposes in solution to give the corresponding hydroxo-bridged complex [(η6-indane)Ru(μ-OH)3Ru(η6-C6Me6)]+ (2) with retention of the asymmetrical geometry as shown by single-crystal X-ray structure analysis. The indane ligand adopts an envelope conformation toward the ruthenium atom.
  • Publication
    Accès libre
    Synthesis of a trinuclear cation [H3Ru3(Fc-arene)(C6Me6)2(O)]+ containing a ferrocenyl group tethered to an arene ligand
    (2003-11-20)
    Vieille-Petit, Ludovic
    ;
    Unternährer, Sabine
    ;
    Therrien, Bruno 
    ;
    Süss-Fink, Georg 
    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.
  • Publication
    Accès libre
    Chiral Arene Ruthenium Complexes : Synthesis and Molecular Structure of the Enantiopure Cluster Cation (S)-[H3Ru3{C6H5[CH(CH3)CH2OH]}(C6Me6)2(O)]+
    (2003)
    Vieille-Petit, Ludovic
    ;
    Therrien, Bruno 
    ;
    Süss-Fink, Georg 
    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.