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Global and local charge transfer in electron donor-acceptor complexes

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Abstract

The formation of electron donor-acceptor complexes is studied with global and local charge transfer partitionings. The 1-parabola model is applied to the bromination reaction of alkenes and the correlations found between the global and local charge transferred with the transition energy of the charge transfer bands and the kinetic rate constants indicate that the nucleophilic attack of alkenes to bromine is the electronic process controlling the reactivity in the formation of the electron donor-acceptor complexes in this reaction. The 2-parabolas model is used in studying the nitrosation of aromatic compounds where colorful electron donor-acceptor complexes are formed. In this case, and like previous applications of the 2-parabolas model, the consistent usage of the model mandates the explicit consideration of reaction conditions in preparing the reactants to have a direction of electron transfer that is consistent with the chemical potential differences. For the nitrosation reaction this implies considering the nitrosonium cation as the charge acceptor. Both applications support that the charge transferred predicted from chemical reactivity models can be used as a scale to measure the nucleophilicity in reactivity trends.

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Acknowledgments

We thank the Cluster Híbrido Xiuhcoatl from Cinvestav and Laboratorio Nacional de Cómputo de Alto Desempeño (LANCAD) for providing computer time for this project. JLG thanks Conacyt for grant 237045, and AV thanks Conacyt for grant Fronteras 867. It is our great honor and pleasure to dedicate this contribution to the celebration of the 60th birthday of our great friend Prof. Pratim Chatarraj, with whom we have always enjoyed enlightening discussions and his deep thoughts about chemical reactivity within DFT. We wish him many more years of a happy, healthy, and scientifically productive life.

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  1. Departamento de Química, Centro de Investigación y de Estudios Avanzados, Av. Instituto Politécnico Nacional 2508, D. F. 07360, México, Mexico

    Ulises Orozco-Valencia & Alberto Vela

  2. Departamento de Química, Universidad Autónoma Metropolitana-Iztapalapa, Av. San Rafael Atlixco 186, 09340, Ciudad de México, Mexico

    José L. Gázquez

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  1. Ulises Orozco-Valencia
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Correspondence to Alberto Vela.

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This paper belongs to Topical Collection International Conference on Systems and Processes in Physics, Chemistry and Biology (ICSPPCB-2018) in honor of Professor Pratim K. Chattaraj on his sixtieth birthday

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Orozco-Valencia, U., Gázquez, J.L. & Vela, A. Global and local charge transfer in electron donor-acceptor complexes. J Mol Model 24, 250 (2018). https://doi.org/10.1007/s00894-018-3772-y

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