The joint application of experimental techniques, such as MIKE, CAD, and FT-ICR spectrometry, and computational methods (DFT and QCISD(T)) has allowed preparation and characterization of gaseous XeNO3+ and XeNO2+ ions. The most stable structure of XeNO3+ has the XeONO2 connectivity, with a relatively short (2.088 Å) Xe−O bond, and represents the gas-phase counterpart of Xe(II) nitrate, previously observed in solution. The XeNO2+ cation is best characterized as a [Xe−NO2]+ complex, with a large (3.018 Å) Xe−NO2 separation and a relatively low dissociation energy, 10.8 kcal mol-1. The reaction of XeNO3+ with selected nucleophiles, including CH3OH, C2H5NO2, CH3COCH3, CH3CN, and C2H5CN, investigated by FT-ICR mass spectrometry, characterizes the ion as a nitrating agent. The unimolecular and collision-induced fragmentation of XeNO3+ and XeNO2+ is discussed.
XeNO3+: a gaseous cation characterized by a remarkably strong Xe-O bond / F., Bernardi; Cacace, Fulvio; DE PETRIS, Giulia; I., Rossi; Pepi, Federico. - In: JOURNAL OF PHYSICAL CHEMISTRY. A, MOLECULES, SPECTROSCOPY, KINETICS, ENVIRONMENT, & GENERAL THEORY. - ISSN 1089-5639. - STAMPA. - 102:29(1998), pp. 5831-5831. [10.1021/jp980781e]
XeNO3+: a gaseous cation characterized by a remarkably strong Xe-O bond.
CACACE, Fulvio;DE PETRIS, GIULIA;PEPI, Federico
1998
Abstract
The joint application of experimental techniques, such as MIKE, CAD, and FT-ICR spectrometry, and computational methods (DFT and QCISD(T)) has allowed preparation and characterization of gaseous XeNO3+ and XeNO2+ ions. The most stable structure of XeNO3+ has the XeONO2 connectivity, with a relatively short (2.088 Å) Xe−O bond, and represents the gas-phase counterpart of Xe(II) nitrate, previously observed in solution. The XeNO2+ cation is best characterized as a [Xe−NO2]+ complex, with a large (3.018 Å) Xe−NO2 separation and a relatively low dissociation energy, 10.8 kcal mol-1. The reaction of XeNO3+ with selected nucleophiles, including CH3OH, C2H5NO2, CH3COCH3, CH3CN, and C2H5CN, investigated by FT-ICR mass spectrometry, characterizes the ion as a nitrating agent. The unimolecular and collision-induced fragmentation of XeNO3+ and XeNO2+ is discussed.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
