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dc.contributor.CRUESPUniversidade Estadual de Campinaspt_BR
dc.typeArtigo de periódicopt_BR
dc.titleLocating the charge site in heteroaromatic cationspt_BR
dc.contributor.authorCarvalho, Mpt_BR
dc.contributor.authorGozzo, FCpt_BR
dc.contributor.authorMendes, MApt_BR
dc.contributor.authorSparrapan, Rpt_BR
dc.contributor.authorKascheres, Cpt_BR
dc.contributor.authorEberlin, MNpt_BR
unicamp.authorUNICAMP, State Univ Campinas, Inst Chem, BR-13083970 Campinas, SP, Brazilpt_BR
dc.subjectab initio calculationspt_BR
dc.subjectcollision-induced dissociationpt_BR
dc.subjectin-molecule reactionspt_BR
dc.subjectmass spectrometrypt_BR
dc.subject.wosSoot Formationpt_BR
dc.description.abstractLow-energy collision-induced dissociation (CID) and ion-molecule reactions with 2-methyl-1,3-dioxolane (MD) performed by pentaquadrupole (QqQqQ) mass spectrometry were applied to locate the charge site in isomeric heteroaromatic cations. The 2-, 3-, and 4-pyridyl cations are indistinguishable by CID. However, as suggest ed by MS3 experiments and ab initio calculations, the 2-pyridyl cation reacts extensively with MD by a transacetalization-like mechanism to afford a bicyclic dihydrooxazolopyridyl cation. The 3- and 4-pyridyl cations, on the contrary react predominantly with MD by proton transfer, as does the analogous phenyl cation. The 2-. 4-, and 5-pyrimidyl cations display characteristic CID behavior. In addition, the 2-pyrimidyl cation reacts extensively with MD by the transacetalization-like mechanism, whereas proton transfer occurs predominantly for the 4- and 5-pyrimidyl cations. The ions thought to be the 2- and 3-furanyl and 2- and 3-thiophenyl cations show indistinguishable CID and ion-molecule behavior. This is most likely the result of their inherent instability in the gas phase and their spontaneous isomerization to the corresponding butynoyl and butynethioyl cations HC=CHCH2C=O+ and HC=CHCH2C=S+. These isomerizations, which are considerably exothermic according to G2(MP2) ab initio calculations, are indicated by a series of experimental results. The ions dissociate upon CID by loss of CO or CS and undergo transacetalization with MD. Most informative is the participation of HC=CHCH2C=S+ in a transacetalization/dissociation sequence with replacement of sulfur by oxygen, which is structurally diagnostic for thioacylium ions. It is therefore possible to locate the charge site of the 2-pyridyl and the three 2-, 4-, and 5-pyrimidyl cations and to identify the isomeric precursors from which they are derived. However, rapid isomerization to the common HC=CHCH2-C=O(S)(+) ion eliminates characteristic chemical behavior that could result from different charge locations in the heteroaromatic 2- and 3-furanyl and 2- and 3-thiophenyl
dc.relation.ispartofChemistry-a European Journalpt_BR
dc.relation.ispartofabbreviationChem.-Eur. J.pt_BR
dc.publisherWiley-v C H Verlag Gmbhpt_BR
dc.identifier.citationChemistry-a European Journal. Wiley-v C H Verlag Gmbh, v. 4, n. 7, n. 1161, n. 1168, 1998.pt_BR
dc.sourceWeb of Sciencept_BR
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