Now showing 1 - 10 of 14
  • Publication
    Open Access
    Remarkable Anticancer Activity of Triruthenium-Arene Clusters Compared to Tetraruthenium-Arene Clusters
    (2007) ;
    Ang, Wee Han
    ;
    Chérioux, Frédéric
    ;
    Vieille-Petit, Ludovic
    ;
    Juillerat-Jeanneret, Lucienne
    ;
    ;
    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
    Open Access
    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) ;
    Vieille-Petit, Ludovic
    ;
    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
    Open Access
    X-ray crystallographic study of two dinuclear triply-bridged p-cymene osmium complexes
    (2005) ;
    Vieille-Petit, Ludovic
    ;
    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
    Open Access
    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) ;
    Vieille-Petit, Ludovic
    ;
    ;
    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
    Open Access
    Ruthenium(II) complexes with ferrocene-modified arene ligands: synthesis and electrochemistry
    (2004) ;
    Vieille-Petit, Ludovic
    ;
    Jeanneret-Gris, Julie
    ;
    Štěpnička, Petr
    ;
    A series of arene–ruthenium complexes of the general formula [RuCl26-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 RuCl3nH2O to afford [RuCl26-C6H5 (CH2)2OC(O)Fc}]2, and (b) esterification between ferrocene carboxylic acid and [RuCl26-C6H5 (CH2)3OH}L] to give [RuCl26-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 [RuCl26-C6H5 (CH2)3OH}(PPh3)] shows that the presence of a CH2CH2CH2OH side-arm allows [RuCl26-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
    Open Access
    An asymmetric trihydrido-bridged arene ruthenium complex
    (2004)
    Vieille-Petit, Ludovic
    ;
    ;
    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
    Open Access
    2,3,4,7-Tetrahydro-1H-inden-2-ol: synthesis, molecular structure and coordination chemistry
    (2004)
    Vieille-Petit, Ludovic
    ;
    ;
    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 RuCl3nH2O in refluxing ethanol to afford [Ru(arene)Cl2]2 (4) (arene=ferrocene carboxylic acid indan-2-yl ester) as a mixture of isomers.
  • Publication
    Open Access
    Supramolecular cluster catalysis : facts and problems
    (2004) ; ;
    Vieille-Petit, Ludovic
    ;
    Tschan, Mathieu J.-L.
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    Romakh, Vladimir B.
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    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
    Open Access
    Synthesis and molecular structure of the trinuclear ruthenium cluster cations [H3Ru3{C6H5(CH2)2OC(O)C6H5}(C6Me6)2(O)]+ and [H3Ru3{C6H5(CH2)2OC(O)(CH2)3C6H5}(C6Me6)2(O)]+
    (2004)
    Vieille-Petit, Ludovic
    ;
    ;
    Benzoic acid 2-cyclohexa-1,4-dienyl ethyl ester (1), and 4-phenylbutyric acid 2-cyclohexa-1,4-dienyl ethyl ester (2) are prepared by reacting, respectively, benzoic acid and 4-phenylbutyric acid with 2-cyclohexa-1,4-dienyl ethanol. These dienyl ester derivatives react with RuCl3n H2O in refluxing ethanol to afford in good yield [Ru{C6H5(CH2)2OC(O)C6H5}Cl2] 2 (3), and [Ru{C6H5(CH2)2OC(O)(CH2)3C6H5}Cl2]2 (4). The trinuclear arene–ruthenium cluster cations [H3Ru3{C6H5 (CH2)2OC(O)C6H5}(C6Me6)2(O)]+ (5), and [H3Ru3{C6H5(CH2)2OC(O)(CH2)3C6H5}(C6Me6)2(O)]+ (6) are synthesised from the dinuclear precursor [H3Ru2(C6Me6)2]+, and the mononuclear complexes [Ru{C6H5(CH2)2OC(O)C6H5}(H2O)3]2+ and [Ru{C6H5(CH2)2OC(O)(CH2)3C6H5}(H2O)3]2+, accessible, respectively, from 3 and 4 in aqueous solution. The water-soluble trinuclear cluster cations 5, and 6 possess a phenyl substituent attach to their side-arm which can act as a substrate for hydrogenation. The single-crystal X-ray structure analyses of [5][PF6], and [6][PF6] have been determined.
  • Publication
    Open Access
    Host–guest properties of the trinuclear arene–ruthenium cluster cation [H3Ru3(C6H6)(C6Me6)2(O)]+
    (2004) ;
    Vieille-Petit, Ludovic
    ;
    The trinuclear arene–ruthenium cluster cation [H3Ru3(C6H6)(C6Me6)2(O)]+, containing a μ3-oxo cap and three arene ligands that span a hydrophobic pocket above the metal skeleton, has been crystallised as tetrafluoroborate salt in the presence of various guest molecules. The host–guest complexes have been characterised by single-crystal X-ray structure analysis. With chloroform as the guest molecule, a CHCl3 molecule sits perfectly in the hydrophobic pocket, the hydrogen atom being encapsulated inside the cavity. When dioxane is added during the crystallisation process, the cluster forms infinite chains which are connected by a complex network of hydrogen bonds involving the μ3-oxo ligand, water and dioxane molecules. Interestingly, in the presence of phenol, a water molecule is hydrogen-bonded between the μ3-oxo ligand and the phenol molecule, forming a one-dimensional μ3-O … H2O … HO hydrogen-bonded chain. Finally, with benzoic acid, a head-to-tail host–guest chain is obtained, the phenyl ring being incorporated in the hydrophobic pocket, while the acid group is hydrogen-bonded to the μ3-oxo ligand.