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dc.creatorAlmeida, Katia Julia de-
dc.creatorSilva, T. C.-
dc.creatorLeal Neto, Jonas-
dc.creatorRocha, M. V. J.-
dc.creatorRamalho, T. C.-
dc.creatorMiranda, M. N. de-
dc.creatorDuarte, Hélio Anderson-
dc.date.accessioned2018-11-21T15:47:17Z-
dc.date.available2018-11-21T15:47:17Z-
dc.date.issued2016-01-
dc.identifier.citationALMEIDA, K. J. de et al. Methane C–H bond activation by niobium oxides: theoretical analyses of the bonding and reactivity properties of NbOn+m (m = 1, 2; n = 0, 1, 2). Journal of Organometallic Chemistry, [S.l.], v. 802, p. 49-59, Jan. 2016.pt_BR
dc.identifier.urihttps://www.sciencedirect.com/science/article/pii/S0022328X15302102pt_BR
dc.identifier.urihttp://repositorio.ufla.br/jspui/handle/1/31863-
dc.description.abstractThe catalytic properties of (m = 1, 2; n = 0, 1, 2) on the methane C–H bond activation were investigated using B3LYP and CCSD(T) calculations. The spin–orbit relativistic effects were evaluated by means of ZORA approximations. The main results indicate that in agreement with the previous experimental findings only the neutral NbO monoxide is kinetically and thermodynamically feasible via the oxidative addition, whereas the remaining oxides and dioxides show better theoretical predictions in the hydrogen abstraction pathways. In these reactions, a known mechanism described as “Oxidative Hydrogen Migration (OHM)” was found to be more stable for the neutral and singly charged niobium-oxo species, while competitive direct H abstraction (DHA) and OHM pathways were obtained for the doubly charged niobium oxides, with slightly preferential conditions observed in DHA. Overall, the increase of charge on the metal center and the presence of the oxo ligands favors the initial electrostatic interaction between niobium oxides and methane, decreasing the activation barrier heights in the H abstraction pathways due to the electron acceptor nature of oxo ligands. Among the investigated oxides, NbO2+ and show the best performances in the methane activation process, with activation barriers computed to be around 1.5–5.9 kcal mol−1.pt_BR
dc.languageen_USpt_BR
dc.publisherElsevierpt_BR
dc.rightsrestrictAccesspt_BR
dc.sourceJournal of Organometallic Chemistrypt_BR
dc.titleMethane C–H bond activation by niobium oxides: theoretical analyses of the bonding and reactivity properties of NbOn+m (m = 1, 2; n = 0, 1, 2)pt_BR
dc.typeArtigopt_BR
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