2024-03-28T13:48:07Zhttp://uvadoc.uva.es/oai/requestoai:uvadoc.uva.es:10324/226102021-06-23T11:52:40Zcom_10324_1186com_10324_931com_10324_894col_10324_1404
Halogen-abstraction reactions from chloromethane and bromomethane molecules by alkaline-earth monocations
Redondo Cristóbal, María del Pilar
Largo Cabrerizo, Antonio
Rayón Rico, Víctor Manuel
Molpeceres de Diego, Germán
Sordo, José Ángel
Barrientos Benito, María Carmen
Producción Científica
The reactions, in the gas phase, between alkali-earth monocations (Mg(+), Ca(+), Sr(+), Ba(+)) and CH3X (X = Cl, Br) have been theoretically studied. The stationary points on the potential energy surfaces were characterized at the Density Functional Theory level on the framework of the mPW1K functional with the QZVPP Ahlrichs's basis sets. A complementary kinetics study has also been performed using conventional/variational microcanonical transition state theory. In the reactions of Mg(+) with either chloro- or bromomethane the transition structure lies in energy clearly above the reactants rendering thermal activation of CH3Cl or CH3Br extremely improbable. The remaining reactions are exothermic and barrierless processes; thus carbon-halogen bonds in chloro- or bromomethane can be activated by calcium, strontium or barium monocations to obtain the metal halogen cation and the methyl radical. The Mulliken population analysis for the stationary points of the potential energy surfaces supports a "harpoon"-like mechanism for the halogen-atom abstraction processes. An analysis of the bonding situation for the stationary points on the potential energy surface has also been performed in the framework of the quantum theory of atoms in molecules
2017-03-14
2017-03-14
2014
info:eu-repo/semantics/article
Physical Chemistry Chemical Physics 2014 Aug 14;16(30), p. 16121-36
1463-9076
http://uvadoc.uva.es/handle/10324/22610
10.1039/c4cp02094d
Physical Chemistry Chemical Physics
eng
http://pubs.rsc.org
info:eu-repo/semantics/openAccess
http://creativecommons.org/licenses/by-nc-nd/4.0/
© The Royal Society of Chemistry
Attribution-NonCommercial-NoDerivatives 4.0 International
Royal Society of Chemistry