R(Ar)O-N-2(+) vs. R(Ar)-N2O+: Are alkoxy-(aryloxy-)diazonium ions or alkyl-(aryl-)N-nitroso-onium ions formed in the gas-phase reactions of N2O with H+, Me+, Ph+, PhCH2+, Tr+ and PhCO+?

dc.creatorCabrini, LG
dc.creatorBenassi, M
dc.creatorEberlin, MN
dc.creatorOkazaki, T
dc.creatorLaali, KK
dc.date2007
dc.date36892
dc.date2014-11-20T00:15:09Z
dc.date2015-11-26T18:07:58Z
dc.date2014-11-20T00:15:09Z
dc.date2015-11-26T18:07:58Z
dc.date.accessioned2018-03-29T00:50:05Z
dc.date.available2018-03-29T00:50:05Z
dc.identifierEuropean Journal Of Organic Chemistry. Wiley-v C H Verlag Gmbh, n. 1, n. 70, n. 77, 2007.
dc.identifier1434-193X
dc.identifierWOS:000243303000008
dc.identifier10.1002/ejoc.200600679
dc.identifierhttp://www.repositorio.unicamp.br/jspui/handle/REPOSIP/58774
dc.identifierhttp://www.repositorio.unicamp.br/handle/REPOSIP/58774
dc.identifierhttp://repositorio.unicamp.br/jspui/handle/REPOSIP/58774
dc.identifier.urihttp://repositorioslatinoamericanos.uchile.cl/handle/2250/1293713
dc.descriptionGas-phase reactions of N2O with H+, Me+, Ph+, PhCH2+, Tr+ (the tropylium. ion) and PhCO+ were studied by pentaquadrupole mass spectrometry. Collision-induced dissociation (CID) of the product ions establishes that, in the diluted solvent and counterion-free MS environment, gaseous Me+ and Ph+ ions form preferentially Me(Ph)O-N-2(+) (electrophilic attack at oxygen), whereas PhCH2+ forms preferentially PhCH2-N2O+ (electrophilic attack at nitrogen). The nascent phenoxydiazonium. ion PhO-N-2(+) dissociates promptly by N-2 loss to form PhO+ as the observable addition product. The PhCO+ and Tr+ ions are unreactive towards addition to N2O. The CID and ion/molecule chemistry of [N2O + H](+) are in conclusive with regard to connectivity, because the ion is rather resistant towards dissociation and reacts essentially as a proton donor species. Gaseous MeO-N-2(+) is not only efficient as a methylating agent towards ethers, heteroaromatics and nitriles, but also displays a rich chemistry that includes polar [4+2(+)] stepwise cycloadditions with representative dienes and polar transacetalization with cyclic acetals. Relative energies and geometries of various RO-N-2(+)/R-N2O+ isomeric pairs were evaluated by MP2 and DFT calculations. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007).
dc.description1
dc.description70
dc.description77
dc.languageen
dc.publisherWiley-v C H Verlag Gmbh
dc.publisherWeinheim
dc.publisherAlemanha
dc.relationEuropean Journal Of Organic Chemistry
dc.relationEur. J. Org. Chem.
dc.rightsfechado
dc.rightshttp://olabout.wiley.com/WileyCDA/Section/id-406071.html
dc.sourceWeb of Science
dc.subjectalkoxy-(aryloxy-)diazonium ions
dc.subjectalkyl-(aryl-)N-nitroso-onium ions
dc.subjection-molecule reactions
dc.subjectpentaquadrupole mass spectrometry
dc.subjectpolar cycloadditions
dc.subjectpolar transacetalization
dc.subjectMass-spectrometry
dc.subjectIon/molecule Reactions
dc.subjectSpectroscopic Detection
dc.subjectBenzyl Azoxytosylate
dc.subjectAromatic-compounds
dc.subjectProtonated N2o
dc.subjectNitrous-oxide
dc.subjectSolvolysis
dc.subjectTransacetalization
dc.subjectChemistry
dc.titleR(Ar)O-N-2(+) vs. R(Ar)-N2O+: Are alkoxy-(aryloxy-)diazonium ions or alkyl-(aryl-)N-nitroso-onium ions formed in the gas-phase reactions of N2O with H+, Me+, Ph+, PhCH2+, Tr+ and PhCO+?
dc.typeArtículos de revistas


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