DFT study of the reaction between VO2+ and C2H6

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dc.contributor.authorGracia, L.
dc.contributor.authorAndres, J.
dc.contributor.authorSafont, V. S.
dc.contributor.authorBeltran, A.
dc.contributor.institutionUniv Jaume 1
dc.contributor.institutionUniversidade Estadual Paulista (Unesp)
dc.date.accessioned2014-05-20T15:29:45Z
dc.date.available2014-05-20T15:29:45Z
dc.date.issued2004-02-16
dc.description.abstractThe molecular mechanisms of the reaction VO2+ ((1)A(1)/(3)A'') + C2H6 ((1)A(g)) to yield V(OH)(2)(+) ((1)Sigma(+)/(3)Sigma(-)) + C2H4 ((1)A(g)) and/or VO+ ((1)Delta/(3)Sigma) + H2O ((1)A(1)) + C2H4 (Ag-1) have been investigated with density functional theory (DFT) at the B3LYP/6-311G(2d,p) level. Calculations including geometry optimization, vibrational analysis, and Gibbs free energy for the stationary points on the reactive potential energy surfaces at both the singlet (s) and first excited triplet (t) electronic states have been carried out. The most thermodynamically and kinetically favorable pathway is the formation of t-V(OH)(2)(+) + C2H4 along a four-step molecular mechanism (insertion, two consecutive hydrogen transfers, and elimination). A crossing point between s and t electronic states has been characterized. A comparison with previous works on VO2+ + C2H4 (Gracia et al. J. Phys. Chem. A 2003, 107, 3107-3120) and VO2+ + C3H8 (Engeser et al. Organometallics 2003, 22, 3933-3943) reactions allows us a rationalization of the different reactivity patterns. The catalytic role of water molecules in the tautomerization process between hydrated oxide cation, VO(H2O)(+,) and dihydroxide cation, V(OH)(2)(+), is achieved by a water-assisted mechanism.en
dc.description.affiliationUniv Jaume 1, Dept Ciências Expt, Castellon de La Plana 12080, Spain
dc.description.affiliationUniv Estadual Paulista, Lab Simulacao Mol, BR-17033360 Bauru, SP, Brazil
dc.description.affiliationUnespUniv Estadual Paulista, Lab Simulacao Mol, BR-17033360 Bauru, SP, Brazil
dc.format.extent730-739
dc.identifierhttp://dx.doi.org/10.1021/om0342098
dc.identifier.citationOrganometallics. Washington: Amer Chemical Soc, v. 23, n. 4, p. 730-739, 2004.
dc.identifier.doi10.1021/om0342098
dc.identifier.issn0276-7333
dc.identifier.urihttp://hdl.handle.net/11449/39255
dc.identifier.wosWOS:000188872700015
dc.language.isoeng
dc.publisherAmer Chemical Soc
dc.relation.ispartofOrganometallics
dc.relation.ispartofjcr4.051
dc.relation.ispartofsjr1,652
dc.rights.accessRightsAcesso restrito
dc.sourceWeb of Science
dc.titleDFT study of the reaction between VO2+ and C2H6en
dc.typeArtigo
dcterms.licensehttp://pubs.acs.org/paragonplus/copyright/jpa_form_a.pdf
dcterms.rightsHolderAmer Chemical Soc
unesp.author.orcid0000-0001-9684-2568[1]
unesp.author.orcid0000-0003-0232-3957[2]
unesp.author.orcid0000-0003-2709-4230[3]
unesp.author.orcid0000-0001-9665-5527[4]

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