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Süss-Fink, Georg

Nom
Süss-Fink, Georg
Affiliation principale
Fonction
Professeur ordinaire
Email
georg.suess-fink@unine.ch
Identifiants
https://libra.unine.ch/handle/123456789/385

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  • Publication
    Accès libre
    Mesomorphic Metallo-Dendrimers Based on the Metal−Metal Bonded Ru2(CO)4 Sawhorse Unit
    (2008)
    Frein, Stéphane
    ;
    Auzias, Mathieu
    ;
    Sondenecker, Aline
    ;
    Vieille-Petit, Ludovic
    ;
    Guintchin, Boris
    ;
    Maringa, Natacha
    ;
    Süss-Fink, Georg 
    ;
    Barberá, Joaquín
    ;
    Deschenaux, Robert 
    Dinuclear ruthenium complexes containing the stable metal−metal bonded Ru2(CO)4 sawhorse unit with two dendritic carboxylato bridges have been synthesized and characterized. All complexes Ru2(CO)4(O2CR)2L2 (R = R1, R2, R3) containing cyanobiphenyl-based poly(arylester) dendrons of first (R1), second (R2), and third (R3) generation and triphenylphosphine, pyridine, or 4-picoline ligands L proved to be mesomorphic, giving rise to smectic A or smectic A and nematic phases. The supramolecular organization within the smectic A phase is governed by the nature and structure of the mesogenic units and dendritic core. Such materials are of interest for the design of catalytically active anisotropic fluids.
  • Publication
    Accès libre
    Remarkable Anticancer Activity of Triruthenium-Arene Clusters Compared to Tetraruthenium-Arene Clusters
    (2007)
    Therrien, Bruno 
    ;
    Ang, Wee Han
    ;
    Chérioux, Frédéric
    ;
    Vieille-Petit, Ludovic
    ;
    Juillerat-Jeanneret, Lucienne
    ;
    Süss-Fink, Georg 
    ;
    Dyson, Paul J.
    The in vitro activity of a series of ruthenium clusters, [(η6-C6H6)(η6-C6Me6)2Ru3 (μ-H)3 (μ3-O)][BF4], [(η6-C6H6)(η6-1,4-iPrC6H4Me)(η6-C6Me6)Ru3 (μ-H)3 (μ3-O)][BF4], [(η6-C6H6)4Ru4 (μ-H)4][BF4]2, [(η6-C6H5Me)4Ru4 (μ-H)4][BF4]2 and [(η6-C6H6)4Ru4 (μ-H)3 (μ-OH)][Cl]2, has been evaluated against A2780 and A2780cisR ovarian carcinoma cell lines. Both triruthenium clusters are very active compared to ruthenium compounds in general, whereas the tetraruthenium clusters do not display significant cytotoxicities. Since the triruthenium clusters are known to form supramolecular interactions with arenes and other functions, it is possible that such interactions are also important with respect to their mode of biological activity. The X-ray structure analysis of [(η6-C6H5Me)4Ru4 (μ-H)4][PF6]2 is also reported.
  • Publication
    Accès libre
    The water-soluble cluster cation [H3Ru3(C6H6)(C6Me6)2(O)]+: Improved synthesis, aerobic oxidation, electrochemical properties and ligand exchange studies
    (2005)
    Vieille-Petit, Ludovic
    ;
    Tschan, Mathieu J.-L.
    ;
    Süss-Fink, Georg 
    ;
    Laurenczy, Gabor
    ;
    Hagen, Collin M.
    ;
    Finke, Richard G.
    ;
    Geneste, Florence
    ;
    Moinet, Claude
    The synthesis of the trinuclear cluster cation [H3Ru3(C6H6)(C6Me6)2(O)]+ (1) has been considerably improved by changes in the NaBH4 addition step and by introducing chromatographic methods; in addition, the redox and ligand exchange properties of 1 have been studied. Although exposure of an aqueous solution of 1 to air yields the oxidised cluster [H3Ru3(C6H6)(C6Me6)2(O) (OH)]+ (2), cyclic voltammetry of [1][BF4] in acetonitrile reveals a first reversible oxidation step that does not involve 2. Bulk electrolysis of 1 and 2 in the same medium affords only decomposition products. Ligand exchange in 1 takes place only at higher temperatures: by heating a mixture of toluene with an aqueous solution of [1][BF4] (1000:1) to 110 °C for 2 h, the formation of the toluene derivative [H3Ru3(C6H5Me)(C6Me6)2 (O)]+ (3) is observed in small quantities. H/D exchange of 1 with D2O does not occur up to 90 °C; however, in the presence of D2, H/D exchange with 1 is observed to give the deuterated derivative [D3Ru3 (C6H6)(C6Me6)2 (O)]+ (1a). The results provide an improved synthesis of 1, as well as information about its redox and ligand-exchange reactions, results necessary to understand and develop the chemistry of 1.
  • Publication
    Accès libre
    X-ray crystallographic study of hydrogen-bonded systems formed between di- and tricarboxylic acids and the trinuclear cluster cation [H3Ru3(C6H6)(C6Me6)2 (O)]+
    (2005)
    Therrien, Bruno 
    ;
    Vieille-Petit, Ludovic
    ;
    Süss-Fink, Georg 
    The hydrogen-bonded systems formed between 5-bromo-isophthalic and trimesic acid derivatives and the trinuclear arene-ruthenium cluster cation [H3Ru3(C6H6)(C6Me6)2 (O)]+ (1) have been studied in the solid state by single-crystal X-ray structure analysis of the tetrafluoroborate salts. The structure analysis of 5-bromo-isophthalic acid with [1][BF4] shows a 1:1 (acid:cluster) supramolecular system, only one hydroxyl of the acid functions interacting with the μ3-oxo ligand of a cation of 1, the hydroxyl group of the second acid function interacting with a tetrafluoroborate anion. With trimesic acid, a 1:2 (acid:cluster) supramolecular system is formed. Two hydroxyl groups interact with the μ3-oxo ligand of two independent cations of 1, while the remaining hydroxyl group of the third acid function interacts with a tetrafluoroborate anion.
  • Publication
    Accès libre
    X-ray crystallographic study of two dinuclear triply-bridged p-cymene osmium complexes
    (2005)
    Therrien, Bruno 
    ;
    Vieille-Petit, Ludovic
    ;
    Süss-Fink, Georg 
    The single crystal X-ray structure analyses of [Os2(p-cymene)2(μ-H)3]PF6 ([1]PF6) and [Os2 (p-cymene)2 (μ-Cl)3]PF6 ([2]PF6) are presented. The two triple bridged arene osmium complexes show the metal to be in an octahedral geometry, where the p-cymene ligand is facially coordinated and where the bridging ligands (Cl or H) occupy the remaining three coordination sites. In the dinuclear trihydrido complex a strong metal–metal interaction is observed. This is not the case for the trichloro complex where a large metal–metal distance indicates no metal–metal bonding.
  • Publication
    Accès libre
    Agrégats trinucléaires arène-ruthénium en tant que catalyseurs d’hydrogénation: Catalyseurs moléculaires intacts ou précurseurs de nanoparticules métalliques catalytiquement actives ?
    (2005)
    Vieille-Petit, Ludovic
    ;
    Süss-Fink, Georg 
    La présente thèse est consacrée à une étude mécanistique de l’hydrogénation des substrats insaturés en solution aqueuse en présence d’agrégats trinucléaires arèneruthénium, utilisés comme catalyseurs hydrosolubles. Dans le domaine de la catalyse, il est primordial de pouvoir discerner un phénomène catalytique moléculaire homogène (manifesté par des complexes organométalliques) d’un phénomène catalytique métallique hétérogène (manifesté par des nanoparticules, issues d’une dégradation partielle du complexe de départ). Cela permet de mieux comprendre les systèmes catalytiques, leurs modes d’action et d’en améliorer les performances ou la sélectivité. En ce qui concerne les agrégats trinucléaires arèneruthénium du type [H3Ru3(arene)3(O)]+, il avait été préalablement conclu qu’ils agissaient en tant que catalyseurs moléculaires intacts pour les réactions d’hydrogénation en milieu aqueux. Cependant, au travers de cette thèse, après différentes démarches différentes mais complémentaires, il a été montré que ces complexes tétraédriques à coeur « Ru3O » n’agissaient pas en tant que catalyseurs moléculaires pour les réactions d’hydrogénation catalytique : sous pression réductrice d’hydrogène, ces agrégats se décomposent partiellement (environ 5%) pour donner naissance à des nanoagrégats « solubles » hautement actifs, représentant la véritable espèce catalytiquement active.
  • 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
    2,3,4,7-Tetrahydro-1H-inden-2-ol: synthesis, molecular structure and coordination chemistry
    (2004)
    Vieille-Petit, Ludovic
    ;
    Therrien, Bruno 
    ;
    Süss-Fink, Georg 
    2,3,4,7-Tetrahydro-1H-inden-2-ol (1) has been synthesised by Birch reduction of indan-2-ol. A single-crystal X-ray structure analysis of 1 shows the compound to exist as hydrogen-bonded polymers along the c-axis due to the presence of a series of hydrogen-bonds between hydroxo functions. The ferrocene ester derivatives, ferrocene carboxylic acid 2,3,4,7-tetrahydro-1H-inden-2-yl ester (2) and ferrocene carboxylic acid indan-2-yl ester (3) have been prepared by peptidic coupling of ferrocene carboxylic acid with 1 and with indan-2-ol, respectively. The single-crystal X-ray structure analyses of 2 and 3 reveal in both cases the cyclopentadienyl rings to adopt an eclipsed conformation with the indenyl substituent being rotated out of the Cp ester plane by almost 90°, allowing no efficient interaction between the π-system of the Cp ring and the indene moiety. The dienyl derivative 2 reacts with RuCl3 • nH2O in refluxing ethanol to afford [Ru(arene)Cl2]2 (4) (arene=ferrocene carboxylic acid indan-2-yl ester) as a mixture of isomers.