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Theoretical study on the elimination kinetics in the gas phase of allyl methyl compounds

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Abstract

The thermal decomposition kinetics of allyl methyl amine, allyl methyl ether, and allyl methyl sulfide in the gas phase has been studied theoretically using the M06-2x/aug-cc-pVTZ quantum chemical approach. The observed activation parameters are consistent with a concerted unimolecular mechanism involving a non-planar cyclic six-membered transition state. Based on the optimized ground state geometries, a natural bond orbital analysis of donor–acceptor interactions reveals that the stabilization energies corresponding to the electronic delocalization from the lone-pair (LP) non-bonding orbitals on the heteroatom to the neighboring \(\sigma_{{{\text{C2}} - {\text{C3}}}}^{*}\) antibonding orbitals decrease from allyl methyl amine to allyl methyl sulfide. This delocalization fairly explains the increase of occupancies of LP orbitals on the heteroatom from allyl methyl sulfide to allyl methyl amine. The results also suggest that the kinetics of the thermolysis of the studied compounds are dominated by \({\text{LP}}\, \to \,\sigma^{*}\) electronic delocalization effects. Analysis of bond order, bond indices, and synchronicity parameters demonstrates that these reactions proceed through a concerted and slightly asynchronous mechanism.

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Authors and Affiliations

  1. Chemistry Department, Tonekabon Branch, Islamic Azad University, Tonekabon, Iran

    Ahmad Reza Oliaey

  2. Young Researchers and Elite Club, East Tehran Branch, Islamic Azad University, Tehran, Iran

    Abolfazl Shiroudi

  3. Chemistry Department, Shahrood Branch, Islamic Azad University, Shahrood, Iran

    Ehsan Zahedi

  4. Center of Molecular and Materials Modelling, Hasselt University, Agoralaan, Gebouw D, 3590, Diepenbeek, Belgium

    Michael S. Deleuze

Authors
  1. Ahmad Reza Oliaey
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  2. Abolfazl Shiroudi
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  3. Ehsan Zahedi
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  4. Michael S. Deleuze
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Corresponding author

Correspondence to Abolfazl Shiroudi.

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Oliaey, A.R., Shiroudi, A., Zahedi, E. et al. Theoretical study on the elimination kinetics in the gas phase of allyl methyl compounds. Monatsh Chem 149, 1389–1400 (2018). https://doi.org/10.1007/s00706-018-2184-0

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  • DOI: https://doi.org/10.1007/s00706-018-2184-0

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