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Quadricyclane Radical Cation Rearrangements: A Computational Study of the Transformations to 1,3,5-Cycloheptatriene and Norbornadiene
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.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Quantum Chemistry.
2004 (Swedish)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 10, no 3, 681-688 p.Article in journal (Refereed) Published
Abstract [en]

An alternative skeletal rearrangement of the quadricyclane radical cation (Q.+) explains the side products formed in the one-electron oxidation to norbornadiene. First, the bicyclo[2.2.1]hepta-2-ene-5-yl-7-ylium radical cation, with an activation energy of 14.9 kcal mol-1, is formed. Second, this species can further rearrange to 1,3,5-cycloheptatriene through two plausible paths, that is, a multistep mechanism with two shallow intermediates and a stepwise path in which the bicyclo[3.2.0]hepta-2,6-diene radical cation is an intermediate. The multistep rearrangement has a rate-limiting step with an estimated activation energy of 16.5 kcal mol-1, which is 2.8 kcal mol-1 lower in energy than the stepwise mechanism. However, the lowest activation energy is found for the Q.+ cycloreversion to norbornadiene that has a transition structure, in close correspondence with earlier studies, and an activation energy of 10.1 kcal mol-1, which agrees well with the experimental estimate of 9.3 kcal mol-1. The computational estimates of activation energies were done using the CCSD(T)/6-311+G(d,p) method with geometries optimized on the B3LYP/6-311+G(d,p) level, combined with B3LYP/6-311+G(d,p) frequencies.

Place, publisher, year, edition, pages
2004. Vol. 10, no 3, 681-688 p.
Keyword [en]
Radical ions, Rearrangement, Quadricyclane, Density Functional calculations, Electron spin resonance
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:uu:diva-14970DOI: 10.1002/chem.200305067OAI: oai:DiVA.org:uu-14970DiVA: diva2:42741
Available from: 2008-02-01 Created: 2008-02-01 Last updated: 2017-12-11Bibliographically approved

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Salhi-Benachenhou, NessimaLunell, Sten

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