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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
    Dinuclear hexamethylbenzene ruthenium cations containing η1:η2-2-(ferrocenyl)ethen-1-yl ligands: Synthesis, structure, electrochemistry
    (2006)
    Tschan, Mathieu J.-L.
    ;
    Therrien, Bruno 
    ;
    Ludvík, Jiří
    ;
    Štěpnička, Petr
    ;
    Süss-Fink, Georg 
    The cationic ferrocenyl-containing complexes [(η6-C6Me6)2Ru2 (μ-η1:η2-CH–CHFc)2 (μ-H)]+ (3) and [(η6-C6Me6)2Ru2 (μ-PPh2)(μ-η1:η2-CH–CHFc)(μ-H)]+ (4) have been synthesised in ethanol from ethynylferrocene and the dinuclear precursors [(η6-C6Me6)2Ru2 (μ-H)3]+ (1) and [(η6-C6Me6)2Ru2(μ-PPh2)(μ-H)2]+ (2) respectively, and isolated as tetrafluoroborate salts. The spectroscopic data of 3 and 4 as well as the single-crystal X-ray diffraction analysis of [4][BF4] show that the alkyne function of ethynylferrocene has been converted to a σ/π-ethenyl ligand by transfer of a bridging hydride from the diruthenium backbone onto the α-carbon of the triple bond in ethynylferrocene. The ferrocenyl-containing diruthenium compounds [3][BF4] and [4][BF4] as well as their parent compounds [1][BF4] and [2][BF4] have been studied by voltammetric techniques: Whereas 1 shows only an irreversible Ru(II)/Ru(III) oxidation, the phosphido-bridged derivative 2 displays two well-separated one-electron redox processes. In the case of 3 and 4, the ferrocenyl substituents give rise to additional reversible ferrocene/ferrocenium waves.
  • 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
    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.