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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
    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
    Métadonnées seulement
    Synthesis and characterization of tetrahedral Ru3O clusters with intrinsic framework chirality: a chiral probe of the intact cluster catalysis concept. [Erratum to document cited in CA144:088385]
    (2006)
    Vieille-Petit, Ludovic
    ;
    Süss-Fink, Georg 
    ;
    Therrien, Bruno 
    ;
    Ward, Thomas R.
    ;
    Stoeckli-Evans, Helen 
    ;
    Labat, Gaeel
    ;
    Karmazin-Brelot, Lydia
    ;
    Neels, Antonia
    ;
    Buergi, Thomas
    ;
    Finke, Richard G.
    ;
    Hagen, Collin M.
    On page 6112, Figure 9 was missing and Figure 11 appeared twice. The correct Figure 9 is given. [on SciFinder(R)]
  • Publication
    Métadonnées seulement
    Synthesis and Characterization of Tetrahedral Ru3O Clusters with Intrinsic Framework Chirality: A Chiral Probe of the Intact Cluster Catalysis Concept
    (2005)
    Vieille-Petit, Ludovic
    ;
    Süss-Fink, Georg 
    ;
    Therrien, Bruno 
    ;
    Ward, Thomas R.
    ;
    Stoeckli-Evans, Helen 
    ;
    Labat, Gaeel
    ;
    Karmazin-Brelot, Lydia
    ;
    Neels, Antonia
    ;
    Buergi, Thomas
    ;
    Finke, Richard G.
    ;
    Hagen, Collin M.
    Triruthenium mixed-ligand tetrahedral oxo-capped clusters with framework chirality were prepd. by redn. of areneruthenium triaqua dications followed by capping with areneruthenium dimer as racemic mixts.; diastereomeric mixts. were prepd. using chiral ligand; the prepd. complexes hydrogenate 2-acetamidoacrylate with no ee. Reaction of ArRuCl(?-Cl)2ClRuAr and Ar1RuCl(?-Cl)2ClRuAr1 with Ag2SO4 in aq. soln. gave mixt. of [ArRu(OH2)3]2+ and [Ar1Ru(OH2)3]2+, which upon NaBH4 redn. afforded mixed-ligand binuclear complex Ar1Ru(?-H)3RuAr (4, Ar = ?6-C6Me6, Ar1 = ?6-cymene). Reaction of 4 with Ar2RuCl(?-Cl)2ClRuAr2 and H2O gave the trinuclear cluster [(ArRu)(Ar1Ru)(Ar2Ru)(?3-O)(?-H)3]+ (rac-5, Ar2 = ?6-C6H6). Diastereomeric complexes [(ArRu)(Ar1Ru)(Ar*Ru)(?3-O)(?-H)3]+ [(S,R)-7, (R,R)-7; Ar* = (R)-1-phenylethanol] were prepd. by reaction of 4 with [Ar*RuCl(?-Cl)2ClRuAr*] (6). Analogous complex [(ArRu)(Ar1Ru)(Ar3Ru)(?3-O)(?-H)3]+ (8) was prepd. as a racemic mixt. from known (S,S)-Ar3RuCl(?-Cl)2ClRuAr3 [Ar3 = Et (R)-N-acetyl-?-aminobenzeneacetate]; the complex 8 was sepd. into diastereomers by chromatog., the racemization being caused by epimerization of the chiral ?-carbon. The enantiopure diastereomeric triruthenium clusters [(ArRu)(Ar1Ru)(Ar4Ru)(?3-O)(?-H)3]+ [(S,S)-17, (R,S)-17; Ar4 = (R)-N-acetyl-?-aminobenzeneethanol isobutyrate] were finally prepd. from (S,S)-Ar4RuCl(?-Cl)2ClRuAr4 and 4. The chiral Ru3O framework was evidenced by x-ray crystallog., by CD in the UV and IR regions, and by chiral shift reagents in the NMR spectra. To bring evidence for or against the hypothesis of catalytic hydrogenation by intact trinuclear arene ruthenium clusters contg. an oxo cap, catalytic hydrogenation of Me 2-acetamidoacrylate catalyzed by complexes 13 was performed; the complexes showed low catalytic activity and no asym. induction. [on SciFinder(R)]
  • 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
    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
    Métadonnées seulement
    An unsymmetrical trihydrido-bridged arene ruthenium complex
    (2004)
    Vieille-Petit, Ludovic
    ;
    Therrien, Bruno 
    ;
    Süss-Fink, Georg 
    Reaction of [Ru(?6-indan)(H2O)3]2+ and [Ru(?6-C6Me6)(H2O)3]2+ with NaBH4 in water gives a mixt. of three triple hydrido-bridged arene ruthenium cations [(?6-arene)Ru(?-H)3Ru(?6-arene')]+ (arene = indan and hexamethylbenzene; arene' = indan and hexamethylbenzene). After treatment with NaBF4, the three complexes are sepd. by column chromatog. and the unsym. cation [(?6-indan)Ru(?-H)3Ru(?6-C6Me6)][BF4] can be isolated in moderate yield. This cation decomps. in soln. to give the corresponding hydroxo-bridged complex [(?6-indan)Ru(?-OH)3Ru(?6-C6Me6)]+ with retention of the unsym. geometry as shown by single-crystal X-ray anal. The indan ligand adopts an envelope conformation toward the ruthenium atom. [on SciFinder(R)]
  • Publication
    Métadonnées seulement
    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
    ;
    Therrien, Bruno 
    ;
    Süss-Fink, Georg 
    Benzoic acid 2-cyclohexa-1,4-dienyl Et ester (1), and 4-phenylbutyric acid 2-cyclohexa-1,4-dienyl Et ester (2) are prepd. by reacting, resp., benzoic acid and 4-phenylbutyric acid with 2-cyclohexa-1,4-dienyl ethanol. These dienyl ester derivs. react with RuCl3·nH2O 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). 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 synthesized 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, resp., from 3 and 4 in aq. soln. The water-sol. trinuclear cluster cations 5 and 6 possess a Ph substituent attached 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 detd. [on SciFinder(R)]
  • Publication
    Métadonnées seulement
    Supramolecular cluster catalysis: facts and problems
    (2004)
    Süss-Fink, Georg 
    ;
    Therrien, Bruno 
    ;
    Vieille-Petit, Ludovic
    ;
    Tschan, Mathieu
    ;
    Romakh, Vladimir B.
    ;
    Ward, Thomas R.
    ;
    Dadras, Massoud
    ;
    Laurenczy, Gabor
    By checking the chem. underlying the concept of supramol. cluster catalysis the authors identified two major errors in their 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 the authors had ascribed to a reaction with H2O in the presence of ethylbenzene is simply an oxidn. reaction which occurs in the presence of air. (2) The higher catalytic activity obsd. with ethylbenzene, which the authors had erroneously attributed to the open cluster cation 2, was due to the formation of RuO2·nH2O, caused by a hydroperoxide contamination present in ethylbenzene. [on SciFinder(R)]
  • Publication
    Métadonnées seulement
    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 synthesized by Birch redn. of indan-2-ol. A single-crystal x-ray structure anal. of 1 shows the compd. 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 derivs., 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 prepd. by peptidic coupling of ferrocene carboxylic acid with 1 and with indan-2-ol, resp. The single-crystal x-ray structure anal. 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 ?-system of the Cp ring and the indene moiety. The dienyl deriv. 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 mixt. of isomers. [on SciFinder(R)]