A bonding evolution theory study of the reaction between methylidyne radical, CH(X2Π), and cyclopentadiene, C5H6
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Otros documentos de la autoría: Andres, Juan; Safont Villarreal, Vicent Sixte; Oliva, Mónica; Caster, Kacee; Goulay, Fabien
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Título
A bonding evolution theory study of the reaction between methylidyne radical, CH(X2Π), and cyclopentadiene, C5H6Fecha de publicación
2022-02-01Editor
Wiley; Wiley PeriodicalsISSN
0020-7608; 1097-461XCita bibliográfica
J. Andrés, V. S. Safont, M. Oliva, K. L. Caster, F. Goulay, Int. J. Quantum Chem. 2022, 122(11), e26892. https://doi. org/10.1002/qua.26892Tipo de documento
info:eu-repo/semantics/articleVersión
info:eu-repo/semantics/publishedVersionPalabras clave / Materias
Resumen
In the present work, bonding evolution theory (BET) is applied to gain insight about
the complex reaction between methylidyne radical, CH (X2
Π) and cyclopentadiene,
C5H6. The novelty of this work is that all ... [+]
In the present work, bonding evolution theory (BET) is applied to gain insight about
the complex reaction between methylidyne radical, CH (X2
Π) and cyclopentadiene,
C5H6. The novelty of this work is that all reaction pathways take place in the doublet
electronic state and an unpaired electron is always present. Therefore, taking the
aforementioned reaction as explicative example, we have shown how to apply the
BET tool to these kinds of open-shell systems, by splitting the wavefunctions into
the corresponding alpha and beta parts. As an added value, we have included a
point-by-point description of the algorithm we use to make it available for the
readers. Hence, a complete analysis of bond breaking/forming and charge redistribution along the multi-channels connecting reactants to products via the transition
states and intermediates is presented. We show how the BET brings about the representation of the electronic flow in complex molecular rearrangements like the one
herein studied, yielding a transparent rationalization based on the electron density
redistribution. The present study allows us to conclude that along the different processes giving rise to the benzene product, the breaking of a C C sigma bond initiates
the electronic rearrangement in two cases, but not in the third one. The last step in
these processes can be described as an initial weakening of the C H bond with a
quasi-hydride formation and a final retro-transfer of electrons from the quasi-hydride
to the C H bond. On the other hand, in the way to the fulvene product, the breaking
of the C C sigma bond takes place after previous electronic redistribution. Neither
the last step of the fulvene formation process nor the interesting H transfer
described in the second one, can be explai [-]
Publicado en
Int J Quantum Chem.2022;122:e26892Entidad financiadora
Generalitat Valenciana | Ministerio de Ciencia, Innovación y Universidades (Spain) | National Science Foundation | Universitat Jaume I
Código del proyecto o subvención
AICO 2020/329 | PGC2018-094417-B-I00 | CHE-1764178 | UJI-B2019-30
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© 2022 The Authors. International Journal of Quantum Chemistry published by Wiley Periodicals LLC.