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Rearrangement and hydrogen scrambling pathways of the toluene radical cation: A computational study
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Quantum Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Quantum Chemistry.
2008 (English)In: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 112, no 20, 4694-4702 p.Article in journal (Refereed) Published
Abstract [en]

A computational study is undertaken to provide a unified picture for various rearrangement reactions and hydrogen scrambling pathways of the toluene radical cation (1). The geometries are optimized with the BHandHLYP density functional, and the energies are computed with the ab initio CCSD(T) method, in conjunction with the 6-311+G(d,p) basis set. In particular, four channels have been located, which may account for hydrogen scrambling, as they are found to have overall barriers lower than the observed threshold for hydrogen dissociation. These are a stepwise norcaradiene walk involved in the Hoffman mechanism, a rearrangement of 1 to the methylenecyclohexadiene radical cation (5) by successive [1,2]-H shifts via isotoluene radical cations, a series of [ 1,2] -H shifts in the cycloheptatriene radical cation (4), and a concerted norcaradiene walk. In addition, we have also investigated other. pathways such as the suggested Dewar-Landman mechanism, Which proceeds through 5, via two consecutive [1,2]-H shifts. This pathway is, however, found to be inactive as it involves too high reaction barriers. Moreover, a novel rearrangement pathway that connects 5 to the norcaradiene radical cation (3) has also been located in this work.

Place, publisher, year, edition, pages
2008. Vol. 112, no 20, 4694-4702 p.
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:uu:diva-110199DOI: 10.1021/jp711166dISI: 000255905000023OAI: oai:DiVA.org:uu-110199DiVA: diva2:275536
Available from: 2009-11-05 Created: 2009-11-05 Last updated: 2017-12-12Bibliographically approved

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Salhi-Benachenhou, Nessima

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