Proton transfer from 1,4-pentadiene to superoxide radical anion: a QTAIM analysis
<p>We studied the bis-allylic proton transfer<br />reaction from 1,4-pentadiene to superoxide<br />radical anion (O2<br />·־). Minima and<br />transition state geometries, as well as<br />thermochemical parameters were computed<br />at the B3LYP/6-311+G(3df,...
| Main Authors: | , , , |
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| Format: | Article |
| Language: | English |
| Published: |
Universidad Nacional de Colombia
2014-04-01
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| Series: | Revista Colombiana de Química |
| Subjects: | |
| Online Access: | http://www.revistas.unal.edu.co/index.php/rcolquim/article/view/42916 |
| Summary: | <p>We studied the bis-allylic proton transfer<br />reaction from 1,4-pentadiene to superoxide<br />radical anion (O2<br />·־). Minima and<br />transition state geometries, as well as<br />thermochemical parameters were computed<br />at the B3LYP/6-311+G(3df,2p)<br />level of theory. The electronic wave<br />functions of reactants, intermediates,<br />and products were analyzed within the<br />framework of the Quantum Theory of<br />Atoms in Molecules. The results show<br />the formation of strongly hydrogen bonded<br />complexes between the 1,4-pentadien-<br />3-yl anion and the hydroperoxyl<br />radical as the reaction products. These<br />product complexes (PCs) are more stable<br />than the isolated reactants and much<br />more stable than the isolated products.<br />This reaction occurs via pre-reactive<br />complexes which are more stable than<br />the PCs and the transition states. This is<br />in agreement with the fact that the net<br />proton transfer reaction that leads to free<br />products is an endothermic and nonspontaneous<br />process.</p> |
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| ISSN: | 0120-2804 2357-3791 |