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Stoeckli-Evans, Helen
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Stoeckli-Evans, Helen
Affiliation principale
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helen.stoeckli-evans@unine.ch
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Voici les éléments 1 - 10 sur 22
- PublicationAccès libreCarbonate binding to copper(II) in solution: mixed-ligand complex formation and its application to the isolation and separation of the three isomers of [Cu(bpp)(H2O)][ClO4]2 [bpp = 2,6-bis(pyrrolidin-2-yl)pyridine](2002)
; ; The binding of the carbonate anion to [Cu(meso-bpp)(H2O)]2+ and rac-[Cu(bpp)(H2O)]2+ [bpp = 2,6-bis(pyrrolidin-2-yl)pyridine] in aqueous solution has been investigated. Formation constants of the carbonato complexes [Cu(meso-bpp)(CO3)] and rac-[Cu(bpp)(CO3)] (1.02 × 103 M–1 and 1.77 × 103 M–1, respectively, µ= 0.70 M) have been calculated from spectrophotometric measurements. The formation of these Cu2+ complexes can also be used for an improved synthesis and an easy isolation of the three diastereoisomers of bpp. The mixture of [Cu(meso-bpp)(H2O)]2+ and rac-[Cu(bpp)(H2O)]2+ is separated by elution from SP Sephadex C-25, either as hydroxo or carbonato derivatives. rac-[Cu(bpp)(H2O)]2+ is then resolved into the enantiomers [Cu(S,S-bpp)(H2O)]2+ and [Cu(R,R-bpp)(H2O)]2+, again on SP Sephadex C-25, by means of L-(+)-tartrate as chiral eluent. The three stereoisomers, meso-bpp, (S,S)-bpp and (R,R)-bpp are liberated from the corresponding copper(II) complexes by ligand displacement using trans-1,2-diaminocyclohexane-N,N,N’,N’-tetraacetic acid (H4cdta). The structure of the meso isomer was solved by a single crystal X-ray analysis using the perchlorate salt [meso-bppH2][ClO4]2•2H2O. - PublicationAccès libreDinuclear iron, ruthenium and cobalt complexes containing 1,4-dimethyl-1,4,7-triazacyclononane ligands as well as carboxylato and oxo or hydroxo bridges(2006)
; ; - PublicationAccès libreFramework Fluxionality of Organometallic Oxides : Synthesis, Crystal Structure, EXAFS, and DFT Studies on [{Ru(η6-arene)}4Mo4O16] Complexes(2003)
; ; Proust, AnnaReactions of the molybdates Na2MoO4•2 H2O and (nBu4N)2[Mo2O7] with [{Ru(arene)Cl2}2] (arene=C6H5CH3, 1,3,5-C6H3(CH3)3, 1,2,4,5-C6H2(CH3)4) in water or organic solvents led to formation of the triple-cubane organometallic oxides [{Ru(η6-arene)}4Mo4O16], whose crystal and molecular structures were determined. Refluxing triple cubane [{Ru(η6-C6H5CH3)}4Mo4O16] in methanol caused partial isomerization to the windmill form. The two isomers of [{Ru(η6-C6H5CH3)}4Mo4O16] were characterized by Raman and Mo K-edge X-ray absorption spectroscopy (XAS), both in the solid-state and in solution. This triple-cubane isomer was also used as a spectroscopic model to account for isomerization of the p-cymene windmill [{Ru(η6-1,4-CH3C6H4CH(CH3)2)}4Mo4O16] in solution. Using both Raman and XAS techniques, we were then able to determine the ratio between the windmill and triple-cubane isomers in dichloromethane and in chloroform. Density functional calculations on [{Ru(η6-arene)}4Mo4O16] (arene=C6H6, C6H5CH3, 1,3,5-C6H3(CH3)3, 1,4-CH3C6H4CH(CH3)2, C6(CH3)6) suggest that the windmill form is intrinsically more stable, provided the complexes are assumed to be isolated. Intramolecular electrostatic interactions and steric bulk induced by substituted arenes were found to modulate but not to reverse the energy difference between the isomers. The stability of the triple-cubane isomers should therefore be accounted for by effects of the surroundings that induce a shift in the energy balance between both forms. - PublicationAccès libreOxidative functionalisation of alkanes: synthesis, molecular structure and catalytic implications of anionic vanadium(V) oxo and peroxo complexes containing bidentate N,O ligands(1999)
; ; ; Claude, SaturninA mixture of [NBu4][VO3] and pyrazine-2-carboxylic acid (Hpca) in acetonitrile catalysed smoothly the reaction of alkanes RH (R = CH3 or C6H11) with molecular oxygen (from air) and hydrogen peroxide to give the corresponding alkyl hydroperoxide ROOH as the primary product. The oxo and peroxo anions [VO2(pca)2]– and [VO(O2)(pca)2]–, isolated as the tetrabutylammonium or ammonium salts from acetonitrile solution and fully characterised by single crystal structure analyses, are assumed to be involved in the catalytic process. A screening of different N,O ligands showed Hpca to be the best co-catalyst, while anthranilic acid (Hana) proved to be almost inactive. The isolation and crystal structure analysis of the analogous oxo compound [NBu4][VO2(ana)2] showed a fundamental difference in the co-ordination of the bidentate N,O ligands which might explain the different catalytic activities: while in [VO2(pca)2]– the two pca ligands are bonded through a nitrogen and an oxygen atom (N,O co-ordination), in [VO2(ana)2]– the two ana ligands are co-ordinated via two oxygen atoms of the carboxylato group (O,O co-ordination). - PublicationAccès libreTri- and Tetranuclear Mixed-Metal Clusters Containing Alkyne Ligands : Synthesis and Structure of [Ru3Ir(CO)11(RCCR’)]-, [Ru2Ir(CO)9(RCCR’)]-, and [HRu2Ir(CO)9(RCCR’)](1999)
; - PublicationAccès libreNew Diphosphine Ligands Containing Ethyleneglycol and Amino Alcohol Spacers for the Rhodium-Catalyzed Carbonylation of Methanol(2002)
; ; The new diphosphine ligands Ph2PC6H4C(O)X(CH2)2OC(O)C6H4PPh2 (1: X=NH; 2: X=NPh; 3: X=O) and Ph2PC6H4C(O)O(CH2)2O(CH2)2OC(O)C6H4PPh2 (5) as well as the monophosphine ligand Ph2PC6H4C(O)X(CH2)2OH (4) have been prepared from 2-diphenylphosphinobenzoic acid and the corresponding amino alcohols or diols. Coordination of the diphosphine ligands to rhodium, iridium, and platinum resulted in the formation of the square-planar complexes [(PP)Rh(CO)Cl] (6: PP=1; 7: PP=2; 8: PP=3), [(PP)Rh(CO)Cl]2 (9: PP=5), [(P-P)Ir(cod)Cl] (10: PP=1; 11: PP=2; 12: PP=3), [(PP)Ir(CO)Cl] (13: PP=1; 14: PP=2; 15: PP=3), and [(PP)PtI2] (18: PP=2). In all complexes, the diphosphine ligands are trans coordinated to the metal center, thanks to the large spacer groups, which allow the two phosphorus atoms to occupy opposite positions in the square-planar coordination geometry. The trans coordination is demonstrated unambiguously by the single-crystal X-ray structure analysis of complex 18. In the case of the diphosphine ligand 5, the spacer group is so large that dinuclear complexes with ligand 5 in bridging positions are formed, maintaining the trans coordination of the P atoms on each metal center, as shown by the crystal structure analysis of 9. The monophosphine ligand 4 reacts with [{Ir(cod)Cl}2] (cod=cyclooctadiene) to give the simple derivative [(4)Ir(cod)Cl] (16) which is converted into the carbonyl complex [(4)Ir(CO)2Cl] (17) with carbon monoxide. The crystal structure analysis of 16 also reveals a square-planar coordination geometry in which the phosphine ligand occupies a position cis with respect to the chloro ligand. The diphosphine ligands 1, 2, 3, and 5 have been tested as cocatalysts in combination with the catalyst precursors [{Rh(CO)2Cl}2] and [{Ir(cod)Cl}2] or [H2IrCl6] for the carbonylation of methanol at 170 °C and 22 bar CO. The best results (TON 800 after 15 min) are obtained for the combination 2/[{Rh(CO)2Cl}2]. After the catalytic reaction, complex 7 is identified in the reaction mixture and can be isolated; it is active for further runs without loss of catalytic activity. - PublicationAccès libreFixation and spontaneous dehydrogenation of methanol on a triruthenium–iridium framework: synthesis and structure of the cluster anion [HRu3Ir(CO)12(OMe)]–(1999)
; - PublicationAccès libreSaturated and unsaturated triruthenium clusters containing three sterically demanding phosphine ligands : synthesis and structure of [Ru3(CO)9(PCy3)3] and [Ru3H2(CO)6(PCy3)3](1998)
; - PublicationAccès libreTriruthenium–iridium clusters containing alkyne ligands : synthesis, structure, and catalytic implications of [(µ-H)IrRu3(CO)11(µ3-η2-PhC≡CPh)] and [IrRu3(CO)10(µ4-η2-PhC≡CPh)(µ-η2-PhC=CHPh)](1998)
; - PublicationAccès libreThe mixed-metal carbonyl cluster anion [Ru3Ir(CO)13]– : synthesis, molecular structure, fluxionality, reactivity(1997)
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