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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
    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
    Dinuclear ruthenium sawhorse-type complexes containing bridging ligands with ferrocenyl substituents in endo/endo, endo/exo and exo/exo orientations
    (2006)
    Auzias, Mathieu
    ;
    Therrien, Bruno 
    ;
    Labat, Gael
    ;
    Stoeckli-Evans, Helen 
    ;
    Süss-Fink, Georg 
    The dinuclear Ru complexes Ru2(CO)4(OOCC5H4FeC5H5)2L2 (L = py: 1, L = PPh3: 2) were synthesized from Ru3(CO)12, ferrocene carboxylic acid and pyridine or PPh3, resp. The single-crystal x-ray structure anal. reveals for 1 and 2 a Ru2(CO)4 sawhorse backbone with the two ferrocenyl substituents of the two carboxylato bridges being endo/exo with respect to each other in the solid state. With the new pyridine deriv. NC5H4OOCC5H4FeC5H5-4 (4-ferrocenoyloxypyridine) (3) as axial ligand, the complex Ru2(CO)4(OOCC5H4FeC5H5)2(NC5H4OOCC5H4FeC5H5-4)2 (4) was obtained, the single crystal x-ray structure anal. showing an exo/exo orientation of the two carboxylato bridges in the solid state. The endo/endo orientation is found in the solid-state structure of Ru2(CO)4(HNOCC5H4FeC5H5)2(PPh3)2 (5), the two OCNH bridges being transoid with respect to each other; this complex is accessible from Ru3(CO)12, ferrocenamide and PPh3. [on SciFinder(R)]
  • Publication
    Accès libre
    Dinuclear ruthenium sawhorse-type complexes containing bridging ligands with ferrocenyl substituents in endo/endo, endo/exo and exo/exo orientations
    (2006)
    Auzias, Mathieu
    ;
    Therrien, Bruno 
    ;
    Labat, Gaël
    ;
    Stoeckli-Evans, Helen 
    ;
    Süss-Fink, Georg 
    The dinuclear ruthenium complexes Ru2(CO)4(OOCC5H4FeC5H5)2L2 (L = NC5H5: 1, L = PPh3: 2) have been synthesized from Ru3(CO)12, ferrocene carboxylic acid and pyridine or triphenylphosphine, respectively. The single-crystal X-ray structure analysis reveals for 1 and 2 a Ru2(CO)4 sawhorse backbone with the two ferrocenyl substituents of the two carboxylato bridges being endo/exo with respect to each other in the solid state. With the new pyridine derivative NC5H4OOCC5H4FeC5H5 (4-ferrocenoyl pyridine) (3) as axial ligand, the complex Ru2(CO)4(OOCC5H4FeC5H5)2(NC5H4OOCC5H4FeC5H5)2 (4) was obtained, the single crystal X-ray structure analysis showing an exo/exo orientation of the two carboxylato bridges in the solid state. The endo/endo orientation is found in the solid-state structure of Ru2(CO)4(HNOCC5H4FeC5H5)2(PPh3)2 (5), the two OCNH bridges being transoïd with respect to each other; this complex is accessible from Ru3(CO)12, ferrocenamide and triphenylphosphine.
  • Publication
    Accès libre
    Dinuclear manganese complexes containing 1,4-dimethyl-1,4,7-triazacyclononane ligands as well as carboxylato and oxo bridges
    (2006)
    Romakh, Vladimir B.
    ;
    Therrien, Bruno 
    ;
    Karmazin-Brelot, Lydia
    ;
    Labat, Gael
    ;
    Stoeckli-Evans, Helen 
    ;
    Shul’pin, Georgiy B.
    ;
    Süss-Fink, Georg 
    The reaction of 1,4-dimethyl-1,4,7-triazacyclononane (L-Me2) with MnCl2 • 4H2O in acetonitrile gives, in the presence of sodium formate, hydrogen peroxide, triethylamine and KPF6, the dinuclear Mn(III)–Mn(IV) complex cation [(L-Me2)2Mn2 (O) 2 (OOCH)]2+ (1) which crystallises as the hexafluorophosphate salt.The analogous reaction with sodium benzoate, however, yields the dinuclear Mn(III)–Mn(III) complex cation [(L-Me2)2Mn2 (O)(OOCC6H5)2]2+ (2), isolated also as the hexafluorophosphate salt.In the case of sodium acetate, both cations, the Mn(III)–Mn(IV) complex [(L-Me2)2Mn2 (O) 2 (OOCCH3)]2+ (3) and the known Mn(III)–Mn(III) complex [(L-Me2)2Mn2 (O)(OOCCH3)2]2+ (4) are available, depending upon the molar ratio.The single-crystal X-ray structure analyses show for the green crystals of [1][PF6]1.5 [Cl]0.5 • 1.5 H2O and [3][PF6]2 • (CH3)2CO, a Mn–Mn distance of 2.620(2) and 2.628(4) Å, respectively, while for the red-violet crystal of [4][PF6]2, a Mn–Mn distance of 3.1416(8) Å is observed.All four compounds show catalytic activity for the oxidation of isopropanol with hydrogen peroxide in water and in acetonitrile to give acetone in the presence of oxalic or ascorbic acid as co-catalysts.
  • Publication
    Accès libre
    Dinuclear iron, ruthenium and cobalt complexes containing 1,4-dimethyl-1,4,7-triazacyclononane ligands as well as carboxylato and oxo or hydroxo bridges
    (2006)
    Romakh, Vladimir B.
    ;
    Therrien, Bruno 
    ;
    Labat, Gael
    ;
    Stoeckli-Evans, Helen 
    ;
    Shul’pin, Georgiy B.
    ;
    Süss-Fink, Georg 
    The reaction of 1,4-dimethyl-1,4,7-triazacyclononane (L–Me2) with FeSO4 • 7H2O in aqueous ethanol gives, in the presence of sodium carboxylates, hydrogen peroxide, sodium hydroxide and KPF6, the dinuclear Fe(III)–Fe(III) complex cations [(L–Me2)2Fe2(O)(OOCR) 2]2+ (R = H: 1, R = CH3: 2, R = C6H5: 3), which crystallise as the hexafluorophosphate salts. The corresponding reaction with RuCl3 • nH2O does not work, however, the analogous Ru(III)–Ru(III) complex [(L–Me2)2Ru2 (O)(OOCCH3)2]2+ (5) can be synthesised by reacting Ru(dmso)4Cl2 with L–Me2, HCl and air in refluxing ethanol, followed by addition of sodium acetate, the mononuclear intermediate (L–Me2)RuCl3 • H2O (4) being also isolated and characterised. The reaction of L–Me2, sodium acetate, hydrogen peroxide and triethylamine with CoCl2 • 6H2O in acetonitrile yields, however, the hydroxo-bridged Co(III)–Co(III) complex [(L–Me2)2Co2 (OH)(OOCCH3)2]3+ (6). The molecular structures of 2, 5 and 6, solved by single-crystal X-ray structure analyses of the hexafluorophosphate salts, reveal for the orange crystals of [2][PF6]2 a Fe–Fe distance of 3.104(1) Å, for the purple crystals of [5][PF6]2 a Ru–Ru distance of 3.230(1) Å, and for the violet crystals of [6][PF6]3 • (CH3)2CO a Co–Co distance of 3.358(1) Å. All six complexes show catalytic activity for the oxidation of isopropanol with hydrogen peroxide in water to give acetone in the presence of ascorbic acid as co-catalyst.
  • 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
    Mono and oligonuclear vanadium complexes as catalysts for alkane oxidation : synthesis, molecular structure, and catalytic potential
    (2004-01-30)
    Süss-Fink, Georg 
    ;
    Gonzalez Cuervo, Laura
    ;
    Therrien, Bruno 
    ;
    Stoeckli-Evans, Helen 
    ;
    Shul’pin, Georgiy B.
    A series of mono- and oligonuclear vanadium(V) and vanadium(IV) complexes containing various chelating N,O-, N3-, and O2-ligands have been prepared. The biphasic reaction of an aqueous solution of ammonium vanadate and a dichloromethane solution of hexamethylphosphoramide (hmpa) and pyrazine-2-carboxylic acid (pcaH) or pyrazine-2,5-dicarboxylic acid (pdcaH2) or pyridine-2,5-dicarboxylic acid (pycaH2) yields yellow crystals of [VO2 (pca)(hmpa)] (1), [(VO2)2(pdca)(hmpa)2] (2), and [VO2(pycaH)(hmpa)] (3), respectively. The single-crystal X-ray structure analyses reveal 1 and 3 to be mononuclear vanadium(V) complexes, in which a VO2 unit coordinates to one nitrogen and one oxygen atom of a pca or pycaH chelating ligand, and 2 to be a dinuclear vanadium(V) complex, in which two VO2 units are coordinated through one nitrogen and one oxygen atom of a pdca bridging ligand; in the three complexes the vanadium atoms also coordinate to the oxygen atom of a hmpa ligand. The reaction of N,N,N′,N′-tetrakis(2-benzimidazolylmethyl)-2-hydroxo-1,3-diaminopropane (hptbH) and VOSO4 in methanol gives the cationic complex [(VO)4(hptb) 2(μ-O)]4+ (4), which can be crystallized as the perchlorate salt. In this tetranuclear complex, two dinuclear vanadium(IV) units are held together by a μ-oxo bridge. The known complex [VOCl2 (tmtacn)] (5) was synthesized from the reaction of 1,4,7-trimethyl-1,4,7-triazacyclononane (tmtacn) and VCl3 in acetonitrile; the reaction of tetrabutylammonium vanadate with pyro-cathecol (catH2) in acetonitrile gives the known anionic complex [V(cat)3]− (6), in which the vanadium(V) center is bonded to three cat chelating ligands through the oxygen atoms, obtained as the tetrabutylammonium salt. All compounds synthesized are highly efficient oxidation catalysts for the reaction of cyclohexane with air and hydrogen peroxide in the presence of four equivalents of pcaH per vanadium, although the catalytic activity of the complexes containing bulky chelating ligands 4 and 5 is somewhat lower in the initial period of the reaction. During this period the active species are formed from the complexes and final turnover numbers are high. The catecholate ligands of complex 6 may reduce from V(V) to V(IV) in the beginning of the process, thus providing very high initial oxidation rates.
  • Publication
    Métadonnées seulement
    Iron, cobalt, nickel and ruthenium complexes of 2,6-bis(3,4-dihydro-2H-pyrrol-5-yl)pyridine, a pybox analogue
    (2003)
    Cabort, Amel 
    ;
    Michel, Armelle
    ;
    Therrien, Bruno 
    ;
    Stoeckli-Evans, Helen 
    ;
    Bernauer, Klaus
    ;
    Süss-Fink, Georg 
    ;
    Williams, Alan F.
    ;
    Stupka, Gilles
    The coordination of 2,6-bis(3,4-dihydro-2H-pyrrol-5-yl)pyridine (L) to Ni, Ru, Fe, and Co was studied. The reaction with Ni salts gives the Ni(II) complex [Ni(L)2]2+ (1). The reaction of RuCl3 gives only the Ru(II) complex [Ru(L)2]2+ (2). In the case of Fe, both [Fe(L)2]2+ (3) and [Fe(L)2]3+ (4) were synthesized and characterized. In the case of Co, the Co(III) complex [Co(L)2]3+ (5) was obtained, even if a Co(II) salt was used. However, [Co(L)2]2+ (6) can be obtained under N. Mol. structures of 1-5 complexes were detd. by x-ray anal. of the corresponding perchlorate salts; the structure of 3 was solved for both the perchlorate and the tetrachloroferrate(III) salts. All complexes show an octahedral coordination geometry with meridional arrangement of the two tridentate ligands. The electrochem. behavior of 2, 3 and 6 was studied by cyclic voltammetry. Quasi reversible electron transfer is obsd. for the redox pairs FeIII/FeII and CoII/CoI. The reaction shows somewhat weaker reversibility for CoIII/CoII, whereas the reaction of RuIII/RuII is not reversible. The measurements suggest 2,6-bis(3,4-dihydro-2H-pyrrol-5-yl)pyridine (L) to have a higher stabilization of low-valent oxidn. states of Fe and Co than terpyridine. [on SciFinder(R)]
  • Publication
    Métadonnées seulement
    A cluster containing a pyrazole ligand: [Ru3(?-H)(?-N2C3H3)(CO)10]
    (2002)
    Diz, Enrique Lozano
    ;
    Neels, Antonia
    ;
    Therrien, Bruno 
    ;
    Stoeckli-Evans, Helen 
    ;
    Süss-Fink, Georg 
    The title cluster decacarbonyl-1?4C,2?3C,3?3C-?-hydrido-2:3?2H:H-?-pyrazolyl-2:3?2N1:N2-triangulo-triruthenium, [Ru3(?-H)(?-C3H3N2)(CO)10], which contains a pyrazole ligand, was synthesized and characterized, both spectroscopically and crystallog., as a cyclohexane solvate. Crystals are monoclinic, space group I2/a, with a 14.2248(11), b 9.1670(5), c 59.834(5) Å, ? 90.380(9)°; Z = 8 (2 mols./Z), dc = 2.290; R = 0.041, Rw(F2) = 0.107 for 4743 reflections. The mol. structure is very similar to that of the known dimethylpyrazole deriv. [Ru3(?-H){?-N2C3HMe2-3,5}(CO)10]. [on SciFinder(R)]
  • Publication
    Métadonnées seulement
    Ligand dehydrogenation in ruthenium trinitrogen complexes: synthesis, structure and chirality of the cations [Ru(LH4)(L)]2+ [LH4 = 2,6-bis(pyrrolidin-2-yl)pyridine]
    (2002)
    Cabort, Amel 
    ;
    Therrien, Bruno 
    ;
    Stoeckli-Evans, Helen 
    ;
    Bernauer, Klaus
    ;
    Süss-Fink, Georg 
    Reaction of 2,6-bis(pyrrolidin-2-yl)pyridine (LH4) with RuCl3·3H2O in refluxing MeOH/H2O mixts. gives the octahedral complexes [Ru(LH4)(L)]2+, in which one of the two trihapto ligands was dehydrogenated as 2,6-bis(3,4-dihydro-2H-pyrrol-5-yl)pyridine (L), even if LH4 was present in excess. With the three stereoisomers of LH4, [Ru(R,S-LH4)(L)]2+ (meso), [Ru(R,R-LH4)(L)]2+ and [Ru(S,S-LH4)(L)]2+ were isolated as the perchlorate salts and characterized by x-ray structure anal. and by CD spectra. [on SciFinder(R)]