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The study of the PES and the reaction mechanism between ketene and Lithium Carbenoids and the formation of cyclopropanone

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Abstract

We present a theoretical analysis of the reaction mechanisms on Lithium Carbenoids LiCH2X (X = F, Cl y Br) and ketenes at B3LYP/6-311++G(d,p) level at the IRC. We have considered the implicit solvation effects of dichloromethane using the PCM methodology. For the reaction coordinate analysis, we have used the reaction force analysis and the theoretical tools coming from conceptual DFT, NBO populations and NCI. The reaction mechanism has a barrierless step corresponding to the interaction of the carbenoid and the hydrogen of the ketene α carbon and a single kinetic step representing the bonding of the carbon carbenoid to the ketene α carbon, the activation of the reaction proceeds mostly by electrostatic interactions perpendicular to the molecular plane followed by a rotation of the ketene showing the influence of the ionic nature of the carbenoid, and the following formation of the bond with the ketene β carbon atom. All three reactions are highly exothermic leading to a decomposition product that is far lower in energy than the cyclopropanone. The tendency of the reaction barriers is LiCH2Br < LiCH2Cl < LiCH2F, indicating that the bromine carbenoid is the most reactive molecule of this group.

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Acknowledgements

FONDECYT 1170837 awarded by BH.

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  1. QTC, Departamento de Química Física, Pontificia Universidad Católica de Chile, Avenida Vicuña Mackenna 4860, Macul, Santiago, Chile

    Daniel Villablanca, Sasha Gazzari & Bárbara Herrera

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  1. Daniel Villablanca
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  2. Sasha Gazzari
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  3. Bárbara Herrera
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Contributions

Daniel Villablanca did most of the calculations of the PES and figures. Sasha Gazzari did calculations of the electronic properties, dual descriptor and molecular orbitals. Barbara Herrera wrote and proofread the manuscript.

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Correspondence to Bárbara Herrera.

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Villablanca, D., Gazzari, S. & Herrera, B. The study of the PES and the reaction mechanism between ketene and Lithium Carbenoids and the formation of cyclopropanone. Theor Chem Acc 142, 32 (2023). https://doi.org/10.1007/s00214-023-02965-2

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