The chemistry of the title cations was investigated in the gas phase by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry and by theoretical methods. Cl2H+ (1) was obtained from the protonation of Cl2 by gaseous Brønsted acids and the chlorination of HCl by Cl2F+ and XeCl+. The proton affinity (PA) of Cl2 measured by the FT-ICR equilibrium method is 131.4 ± 1 kcal mol-1 at 298 K, which compares with the 132.0 kcal mol-1 value computed at the CCSD(T) level of theory. 1 has the Cl−Cl−H connectivity, as indicated by its 2-fold reactivity as a Brønsted acid and a chlorinating agent, and confirmed by the theoretical results. The FClH+ cation was obtained from the fluorination of HCl by XeF+ and its most stable protomer (2) has the F−Cl−H connectivity, as shown by its behavior as a pure Brønsted acid and by the theoretical results that identify 2 as the global minimum, whereas protomer 3, having the H−F−Cl connectivity, is computed to be less stable by 5.0 kcal mol-1 at the CCSD(T) level of theory, respectively. For lack of sufficiently accurate experimental data, the best estimate of the PA of ClF is 121.0 kcal mol-1, computed at the CCSD(T) level of theory and referred to protonation of the Cl atom.

Elemental chlorine and chlorine fluoride: theoretical and experimental proton affinity and the gas phase chemistry of Cl2H+ and FClH+ ions / Cacace, Fulvio; DE PETRIS, Giulia; Pepi, Federico; M., Rosi; A., Sgamellotti. - In: JOURNAL OF PHYSICAL CHEMISTRY. A, MOLECULES, SPECTROSCOPY, KINETICS, ENVIRONMENT, & GENERAL THEORY. - ISSN 1089-5639. - STAMPA. - 102:51(1998), pp. 10560-10567. [10.1021/jp9831379]

Elemental chlorine and chlorine fluoride: theoretical and experimental proton affinity and the gas phase chemistry of Cl2H+ and FClH+ ions.

CACACE, Fulvio;DE PETRIS, GIULIA;PEPI, Federico;
1998

Abstract

The chemistry of the title cations was investigated in the gas phase by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry and by theoretical methods. Cl2H+ (1) was obtained from the protonation of Cl2 by gaseous Brønsted acids and the chlorination of HCl by Cl2F+ and XeCl+. The proton affinity (PA) of Cl2 measured by the FT-ICR equilibrium method is 131.4 ± 1 kcal mol-1 at 298 K, which compares with the 132.0 kcal mol-1 value computed at the CCSD(T) level of theory. 1 has the Cl−Cl−H connectivity, as indicated by its 2-fold reactivity as a Brønsted acid and a chlorinating agent, and confirmed by the theoretical results. The FClH+ cation was obtained from the fluorination of HCl by XeF+ and its most stable protomer (2) has the F−Cl−H connectivity, as shown by its behavior as a pure Brønsted acid and by the theoretical results that identify 2 as the global minimum, whereas protomer 3, having the H−F−Cl connectivity, is computed to be less stable by 5.0 kcal mol-1 at the CCSD(T) level of theory, respectively. For lack of sufficiently accurate experimental data, the best estimate of the PA of ClF is 121.0 kcal mol-1, computed at the CCSD(T) level of theory and referred to protonation of the Cl atom.
1998
01 Pubblicazione su rivista::01a Articolo in rivista
Elemental chlorine and chlorine fluoride: theoretical and experimental proton affinity and the gas phase chemistry of Cl2H+ and FClH+ ions / Cacace, Fulvio; DE PETRIS, Giulia; Pepi, Federico; M., Rosi; A., Sgamellotti. - In: JOURNAL OF PHYSICAL CHEMISTRY. A, MOLECULES, SPECTROSCOPY, KINETICS, ENVIRONMENT, & GENERAL THEORY. - ISSN 1089-5639. - STAMPA. - 102:51(1998), pp. 10560-10567. [10.1021/jp9831379]
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11573/242971
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