Abstract

RODRIGUEZ-SERRANO, Ángela; DAZA, Martha C; DOERR, Markus  and  VILLAVECES, José Luis. Proton transfer from 1,4-pentadiene to superoxide radical anion: a QTAIM analysis. Rev.Colomb.Quim. [online]. 2012, vol.41, n.3, pp.409-432. ISSN 0120-2804.

We studied the bis-allylic proton transfer reaction from 1,4-pentadiene to superoxide radical anion (O₂.-). Minima and transition state geometries, as well as thermochemical parameters were computed at the B3LYP/6-311+G(3df,2p) level of theory. The electronic wave functions of reactants, intermediates, and products were analyzed within the framework of the Quantum Theory of Atoms in Molecules. The results show the formation of strongly hydrogen bonded complexes between the 1,4-pentadien- 3-yl anion and the hydroperoxyl radical as the reaction products. These product complexes (PCs) are more stable than the isolated reactants and much more stable than the isolated products. This reaction occurs via pre-reactive complexes which are more stable than the PCs and the transition states. This is in agreement with the fact that the net proton transfer reaction that leads to free products is an endothermic and nonspontaneous process.

Keywords : superoxide radical anion; density functional theory; QTAIM; reaction mechanism; proton transfer; 1,4-pentadiene.

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