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Stoeckli-Evans, Helen

Nom
Stoeckli-Evans, Helen
Affiliation principale
Email
helen.stoeckli-evans@unine.ch
Identifiants
https://libra.unine.ch/handle/123456789/470

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  • Publication
    Métadonnées seulement
    The cluster dication [(eta(6)-C6H6)(2)(eta(6)-C6Me6)(4)Ru-8(mu(2)-H)(2)(mu(3)-O)(2)(mu(2)-Cl) (2)](2+): a chloro-bridged framework containing two metal tetrahedra
    (2002)
    Faure, Matthieu
    ;
    Stoeckli-Evans, Helen 
    ;
    Süss-Fink, Georg 
    The title complex was obtained by reacting [(eta(6)-C6H6)(eta(6)-C6Me6)(2)Ru-3(mu(2)-H)(3)(mu(3)-O)(+) with RuCl3 . nH(2)O in aqueous solution. it crystallises as the tetrafluoroborate salt. The cationic cluster is formed of two tetrahedral Ru-4 substructures which are held together by two chloro bridges. (C) 2002 Elsevier Science B.V. All rights reserved.
  • Publication
    Métadonnées seulement
    The cluster dication [H6Ru4(C6H6)(4)](2+) revisited: the first cluster complex containing an intact dihydrogen ligand?
    (2000)
    Süss-Fink, Georg 
    ;
    Plasseraud, Laurent
    ;
    Maisse-Francois, Aline
    ;
    Stoeckli-Evans, Helen 
    ;
    Berke, Heinz
    ;
    Fox, Thomas
    ;
    Gautier, Régis
    ;
    Saillard, Jean-Yves
    A low-temperature H-1-NMR study suggests the tetranuclear cluster dication [H6Ru4(C6H6)(4)](2+) (1) to contain an H-2 ligand that undergoes, upon warming of the solution, an intramolecular exchange with the four hydride ligands at the Ru-4 framework. Whereas two of the three NMR signals at - 120 degrees C in the hydride region show T-1 values in the range 200-300 ms, the least deshielded resonance at delta = - 17.33 ppm exhibits a T-1 value of only 34 ms, characteristic of an H-2 ligand. a re-examination of the single-crystal X-ray structure analysis of the chloride salt of 1 supports this interpretation by a short distance of 1.14(0.15) Angstrom between two hydrogen atoms coordinated as a PI-PI ligand in a side-on fashion to one of the triangular faces of the Ru-4 tetrahedron. The distance between one of the two hydrogen atoms of the H-2 ligand and one of the four hydride ligands is also very short [1.33(0.15) Angstrom], suggesting an additional H-2... H interaction. The presence of this H-3, unit over one of the three Ru-3 faces in 1 may explain the deformation of the Ru-4 skeleton from the expected tetrahedral symmetry. Density functional theory (DFT) calculations on 1 indicate a very soft potential energy surface associated with the respective displacement of the three interacting cofacial hydrogen atoms. In accordance with these results, the cluster dication 1 tends to loose molecular hydrogen to form the cluster dication [H4Ru4(C6H6)(4)](2+) (2). The equilibrium between 1 and 2 can be used for catalytic hydrogenation reactions. (C) 2000 Elsevier Science S.A. All rights reserved.