Please use this identifier to cite or link to this item: http://repositorio.unicamp.br/jspui/handle/REPOSIP/67801
Type: Artigo de periódico
Title: Gas-phase synthesis and characterization of an azaphosphirenium ion: The first N,P-analogue of the aromatic cyclopropenyl cation
Author: Moraes, LAB
Eberlin, MN
Laali, KK
Abstract: The 3-(dimethylamino)-1,1-dimethyl-1H-azaphosphiren-1-ium ion (3), the first member of the hitherto unknown class of azaphosphirenium ions and the first N,P-analogue of the aromatic cyclopropenyl cation, is generated in the gas phase via 70 eV electron ionization and demetalation of a ferriphosphaalkene (1) and rapid cyclization of the incipient phosphavinyl cation (2). Spontaneous cyclization of 2 to 3 is predicted by Beeke3LYP/6311++G(d,p) calculations, and the structure and reactivity of 3 is probed via collision-induced dissociation and ion-molecule reactions performed via pentaquadrupole mass spectrometry. Gaseous 3 fails to coordinate efficiently with nitrogen and oxygen nucleophiles, but it forms stable adduct ions with phosphorus and sulfur nucleophiles. The adducts of 3 with P and S nucleophiles are likely favored by the incorporation of relatively strong and rare P=S and P=P bonds and through extensive charge delocalization involving dimethylamino substituents. With isoprene, an adduct ion is also readily formed presumably via [4 + 2(+)] cycloaddition (followed by spontaneous ring opening), a reaction which is well documented for phosphenium ions both in solution and in the gas phase.
Country: EUA
Editor: Amer Chemical Soc
Rights: fechado
Identifier DOI: 10.1021/om010458p
Date Issue: 2001
Appears in Collections:Unicamp - Artigos e Outros Documentos

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