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Theoretical study of the gas-phase thermolysis reaction of 3,6-dimethyl-1,2,4,5-tetroxane. Methyl and axial-equatorial substitution effects

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Abstract

Organic peroxides are interesting compounds with a broad range of properties from antimalarial and antimicrobial activities to explosive character. In this work the gas-phase thermolysis reaction mechanism of the 3,6-dimethyl-1,2,4,5-tetroxane (DMT) is studied by DFT calculations, considering axial–axial, axial–equatorial, and equatorial–equatorial position isomers. The critical points of the singlet (S) and triplet (T) potential energy surfaces (PES) are calculated. Three mechanisms are considered: i) S-concerted, ii) S-stepwise, and iii) T-stepwise. The first intermediate of the reaction through S-stepwise-PES is a diradical open structure, o, yielding, as products, two molecules of acetaldehyde and one of O2 in the S state. The S-stepwise-mechanism gives exothermic reaction energies (Er) in the three position isomers. The S-concerted mechanism yields very high activation energies (Ea) in comparison with those of the S-stepwise mechanism. In the T-stepwise mechanism, a triplet open structure (T-o) is first considered, yielding an Er 12 kcal mol–1 more exothermic than that of the S-mechanisms. The S-o and T-o are similar in structure and energies; therefore, a crossing from the S- to T-PES is produced at the o intermediate as a consequence of a spin–orbit coupling. The highest Ea is the first step after o intermediate, and thus it is considered the rate limiting step. Therefore, the Er at the T-PES is more in agreement with the Er of the exothermic experimental diperoxide products. Ea, Er, and O···O distances are studied as a function of the number of methyl groups and the position isomerization.

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Notes

  1. This TSX is named TSC in references [14, 15].

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Acknowledgments

The authors thank the “Centro de Supercomputación de Galicia” (CESGA), and “Centro de Servicios de Informática y Redes de Comunicaciones (CSIRC), Universidad de Granada” (Spain) for providing the computing time. The authors are thankful to “Secretaría General de Ciencia y Técnica de la UNNE (Argentina)”. This work was supported by Spanish MCINN and European FEDER grants FIS2016-77692-C2-2P, PCIN-2017-098 and by the regional agency “Junta de Andalucía” for the RNM-264, -363 and -1897 PAI-grants.

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Authors and Affiliations

  1. Laboratorio de Investigaciones en Tecnología Ambiental, Área de Química Física, Facultad de Ciencias Exactas y Naturales y Agrimensura, UNNE, Avda. Libertad 5460, 3400, Corrientes, Argentina

    Alexander G. Bordón, Andrea N. Pila, Mariela I. Profeta, Jorge M. Romero, Lilian C. Jorge & Nelly Lidia Jorge

  2. Instituto Andaluz de Ciencias de la Tierra, CSIC-UGR, Avda. Las Palmeras 4, 18100, Armilla, Granada, Spain

    Claro Ignacio Sainz-Díaz & Alfonso Hernández-Laguna

  3. Université Grenoble Alpes, CEA, CNRS, INAC-SyMMES, 38000, Grenoble, France

    André Grand

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  1. Alexander G. Bordón
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  9. Alfonso Hernández-Laguna
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Correspondence to Alfonso Hernández-Laguna.

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Bordón, A.G., Pila, A.N., Profeta, M.I. et al. Theoretical study of the gas-phase thermolysis reaction of 3,6-dimethyl-1,2,4,5-tetroxane. Methyl and axial-equatorial substitution effects. J Mol Model 25, 217 (2019). https://doi.org/10.1007/s00894-019-4092-6

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