Artículos de revistas
Gas-phase synthesis and characterization of an azaphosphirenium ion: The first N,P-analogue of the aromatic cyclopropenyl cation
Registro en:
Organometallics. Amer Chemical Soc, v. 20, n. 23, n. 4863, n. 4868, 2001.
0276-7333
WOS:000172243200017
10.1021/om010458p
Autor
Moraes, LAB
Eberlin, MN
Laali, KK
Institución
Resumen
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. 20 23 4863 4868