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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

  • Alexander G. Bordón
  • Andrea N. Pila
  • Mariela I. Profeta
  • Jorge M. Romero
  • Lilian C. Jorge
  • Nelly Lidia Jorge
  • Claro Ignacio Sainz-Díaz
  • André Grand
  • Alfonso Hernández-LagunaEmail author
Original Paper
  • 1 Downloads
Part of the following topical collections:
  1. QUITEL 2018 (44th Congress of Theoretical Chemists of Latin Expression)

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.

Keywords

3,6-dimethyl-1,2,4,5-tetroxane Methyl position isomers Gas-phase thermolysis reaction DFT Potential energy surfaces Reaction mechanisms Methyl substitution effect 

Notes

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.

Supplementary material

894_2019_4092_MOESM1_ESM.docx (41 kb)
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Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  • Alexander G. Bordón
    • 1
  • Andrea N. Pila
    • 1
  • Mariela I. Profeta
    • 1
  • Jorge M. Romero
    • 1
  • Lilian C. Jorge
    • 1
  • Nelly Lidia Jorge
    • 1
  • Claro Ignacio Sainz-Díaz
    • 2
  • André Grand
    • 3
  • Alfonso Hernández-Laguna
    • 2
    Email author
  1. 1.Laboratorio de Investigaciones en Tecnología Ambiental, Área de Química Física, Facultad de Ciencias Exactas y Naturales y Agrimensura, UNNECorrientesArgentina
  2. 2.Instituto Andaluz de Ciencias de la Tierra, CSIC-UGRArmillaSpain
  3. 3.Université Grenoble Alpes, CEA, CNRS, INAC-SyMMESGrenobleFrance

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