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Stoeckli-Evans, Helen
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Stoeckli-Evans, Helen
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Professeur.e émérite
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helen.stoeckli-evans@unine.ch
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- PublicationMétadonnées seulementCationic dinuclear arene ruthenium complexes with one hydroxo and two chloro bridges: synthesis and molecular structure of [(p-Me-C6H4 Pr-i)(2)Ru-2(mu-Cl)(2)(mu-OH)][ReO4](2001)
;Fidalgo, Eva Garcia ;Plasseraud, Laurent; The dinuclear complexes (arene)(2)Ru2Cl4 (arene = benzene, p-cymene, durene, hexamethylbenzene) react in aqueous solution to give, in addition to the known cationic trichloro complexes [(arene)(2)Ru-2(mu -Cl)(3)](+), the new dichloro hydroxo cations [(arene)(2)Ru-2(mu -Cl)(2)(mu -OH)](+) which can be isolated as the perrhenate salts. (C) 2001 Published by Elsevier Science B.V. - PublicationMétadonnées seulementThe cluster dication [H6Ru4(C6H6)(4)](2+) revisited: the first cluster complex containing an intact dihydrogen ligand?(2000)
; ;Plasseraud, Laurent ;Maisse-Francois, Aline; ;Berke, Heinz ;Fox, Thomas ;Gautier, RégisSaillard, Jean-YvesA 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.