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SM ISO690:2012 GULYA, Aurelian, NOVITSKY, Ghenadie, RIBLET, Fabrice, HELM, Lothar, MERBACH, Andre E.. Variable pressure (VP) and variable temperature (VT) 19F NMR investigation of molecular exchange mechanisms in octahedral cobalt(II) complexes. In: Physical Methods in Coordination and Supramolecular Chemistry, 27 septembrie - 1 octombrie 2006, Chişinău. Chisinau, Republic of Moldova: 2006, XVII, p. 44. ISBN 978-9975-62-066-6. |
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Physical Methods in Coordination and Supramolecular Chemistry XVII, 2006 |
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Conferința "The XV-th International Conference Physical Methods in Coordination and Supramolecular Chemistry : The XVII-th Reading in memory of Acad. A.Ablov" Chişinău, Moldova, 27 septembrie - 1 octombrie 2006 | ||||||
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The labile cobalt(II) complex [Co(TUF)2(Pic)2] with 4,4,4-trifluoro-1-(2-thienyl)-1,3butanedione (TUF) bidentate and 4-methylpyridine (Pic) monodentate ligands was studied by variable temperature (VT) and variable pressure (VP) 19F NMR. In contrast to the solid state, all the isomers are present in a CD2Cl2 solution. Thermodynamic parameters (ΔH0, ΔS0 and ΔV0) of each isomer with reference to the trans(N)-trans(CF3)-trans isomer were obtained from the fitting of experimental mole fraction values.figureSchematic representation of the five isomers of [Co(TUF)2(Pic)2figureEvolution of the 19F NMR signals of the five isomers of [Co(TUF)2(Pic)2] with increasing temperature.A kinetics investigation of the isomerization processes was performed by lineshape analysis of the spectra using the Kubo-Sack formalism. The suggested bidentate bondrupture mechanism involves the breaking of the weakest Co–O bond (closest to the CF3 withdrawing group) with the TUF ligand. Heterometallic μ3-oxo carboxylate complexes (Fe2Co and Fe2Ni) have been studied by 2D NMR. The magnetic properties of these compounds are compared in the solid state and in the liquid state. |
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