A comparative study of the gas-phase reactions of NO2+ with acetylene and ethylene was performed by using FT-ICR, MIKE, CAD, and NfR/CA mass spectrometric techniques, in conjunction with ab initio calculations at the MP2/6-31+G* level of theory. Both reactions proceed according to the same mechanism, that is, 1,3-dipolar cycloaddition, but yield products of different stability. The C2H2NO2+ adduct from acetylene has an aromatic character and hence is highly stabilized with respect to the C2H4NO2+ adduct from ethylene. Both cycloadducts tend to isomerize into O-nitroso derivatives, that is, nitrosated ketene and nitrosated acetaldehyde, which represent the thermodynamically most stable products from the addition of NO2+ to acetylene and ethylene, respectively. As prototypal examples of the reactivity of free nitronium ions with most simple pi systems, the reactions investigated are useful starting points to model the mechanism of aromatic nitration.

Gas-phase reactions of nitronium ions with acetylene and ethylene: an experimental and theoretical study / F., Bernardi; Cacace, Fulvio; DE PETRIS, Giulia; Pepi, Federico; I., Rossi; Troiani, Anna. - In: CHEMISTRY-A EUROPEAN JOURNAL. - ISSN 0947-6539. - STAMPA. - 6:3(2000), pp. 537-544. [10.1002/(SICI)1521-3765(20000204)6:3<537::AID-CHEM537>3.0.CO;2-I]

Gas-phase reactions of nitronium ions with acetylene and ethylene: an experimental and theoretical study

CACACE, Fulvio;DE PETRIS, GIULIA;PEPI, Federico;TROIANI, Anna
2000

Abstract

A comparative study of the gas-phase reactions of NO2+ with acetylene and ethylene was performed by using FT-ICR, MIKE, CAD, and NfR/CA mass spectrometric techniques, in conjunction with ab initio calculations at the MP2/6-31+G* level of theory. Both reactions proceed according to the same mechanism, that is, 1,3-dipolar cycloaddition, but yield products of different stability. The C2H2NO2+ adduct from acetylene has an aromatic character and hence is highly stabilized with respect to the C2H4NO2+ adduct from ethylene. Both cycloadducts tend to isomerize into O-nitroso derivatives, that is, nitrosated ketene and nitrosated acetaldehyde, which represent the thermodynamically most stable products from the addition of NO2+ to acetylene and ethylene, respectively. As prototypal examples of the reactivity of free nitronium ions with most simple pi systems, the reactions investigated are useful starting points to model the mechanism of aromatic nitration.
2000
01 Pubblicazione su rivista::01a Articolo in rivista
Gas-phase reactions of nitronium ions with acetylene and ethylene: an experimental and theoretical study / F., Bernardi; Cacace, Fulvio; DE PETRIS, Giulia; Pepi, Federico; I., Rossi; Troiani, Anna. - In: CHEMISTRY-A EUROPEAN JOURNAL. - ISSN 0947-6539. - STAMPA. - 6:3(2000), pp. 537-544. [10.1002/(SICI)1521-3765(20000204)6:3<537::AID-CHEM537>3.0.CO;2-I]
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11573/254551
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