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Reactive atomistic simulations of Diels-Alder-type reactions: conformational and dynamic effects in the polar cycloaddition of 2,3-dibromobutadiene radical ions with maleic anhydride

Rivero, Uxia and Turan, Haydar Taylan and Meuwly, Markus and Willitsch, Stefan. (2021) Reactive atomistic simulations of Diels-Alder-type reactions: conformational and dynamic effects in the polar cycloaddition of 2,3-dibromobutadiene radical ions with maleic anhydride. Molecular Physics, 119 (1-2). e1825852.

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Official URL: https://edoc.unibas.ch/80815/

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Abstract

The kinetics, dynamics and conformational specificities for the ionic Diels-Alder reaction (polar cycloaddition) of maleic anhydride with 2,3-dibromobutadiene radical ions have been studied theoretically using multisurface adiabatic reactive molecular dynamics. A competition of concerted and stepwise reaction pathways was found and both the s-cis and s-trans conformers of the diene are reactive. The analysis of the minimum dynamic path of the reaction indicates that both, rotations and vibrations of the reactant molecules are important for driving the system towards the transition state. The rates were computed as k = 5.1 x 10(-14) s(-1) for the s-cis and k = 3.8 x 10(-14) s(-1) for the s-trans conformer of 2,3-dibromobutadiene at an internal temperature of 300 K. The present results are to be contrasted with the neutral variant of the title system in which only the gauche conformer of the diene was found to undergo a considerably slower, concerted and mostly synchronous reaction driven by the excitation of rotations. The results presented here inform detailed experimental studies of the dynamics of polar cycloadditions under single-collision conditions in the gas phase.
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Chemische Physik (Willitsch)
05 Faculty of Science > Departement Chemie > Chemie > Physikalische Chemie (Meuwly)
UniBasel Contributors:Rivero Gonzalez, Uxia Constanza and Turan, Haydar Taylan and Meuwly, Markus and Willitsch, Stefan
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:Taylor & Francis
ISSN:0026-8976
e-ISSN:1362-3028
Note:Publication type according to Uni Basel Research Database: Journal article
Identification Number:
Last Modified:16 Mar 2021 09:41
Deposited On:24 Feb 2021 11:43

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