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Insights into the Photodecomposition of Azidomethyl Methyl Sulfide: A S2/S1 Conical Intersection on Nitrene Potential Energy Surfaces Leading to the Formation of S-Methyl-N-sulfenylmethanimine

  • Manuel Algarra*
    Manuel Algarra
    CQM-Centro de Química da Madeira, Universidade da Madeira, Campus Universitário da Penteada, 9020-105 Funchal, Portugal
    *E-mail: [email protected] (M.A.).
  • Juan Soto*
    Juan Soto
    Department Physical Chemistry, Faculty of Science, University Málaga, 29016 Málaga, Spain
    *E-mail: [email protected] (J.S.).
    More by Juan Soto
  • Luis Pinto da Silva
    Luis Pinto da Silva
    Chemistry Research Unit (CIQUP), Department of Chemistry and Biochemistry, Faculty of Sciences of University of Porto, R. Campo Alegre 697, 4169-007 Porto, Portugal
    LACOMEPHI, GreenUP, Department of Geosciences, Environment and Territorial Planning, Faculty of Sciences of University of Porto, R. Campo Alegre 697, 4169-007 Porto, Portugal
  • M. Soledad Pino-González
    M. Soledad Pino-González
    Department Organic Chemistry, Faculty of Science, University Málaga, 29016 Málaga, Spain
  • J. Enrique Rodríguez-Borges
    J. Enrique Rodríguez-Borges
    Chemistry Research Unit (CIQUP), Department of Chemistry and Biochemistry, Faculty of Sciences of University of Porto, R. Campo Alegre 697, 4169-007 Porto, Portugal
  • Joelle Mascetti
    Joelle Mascetti
    Institut des Sciences Moléculaires, University Bordeaux, 33405 Talence, France
  • Fabien Borget
    Fabien Borget
    Physique des Interactions Ioniques et Moléculaires, Aix Marseille University, 13007 Marseille, France
  • Adel Reisi-Vanani
    Adel Reisi-Vanani
    Department of Physical Chemistry, Faculty of Chemistry, University of Kashan, 87317-51167 Kashan, Iran
  • , and 
  • Rafael Luque*
    Rafael Luque
    Department Organic Chemistry, University Córdoba, Edif. Marie Curie, Ctra N IVa Km 396, 14014 Córdoba, Spain
    Peoples Friendship University of Russia (RUDN University), 6 Miklukho Maklaya str., 117198 Moscow, Russia
    *E-mail: [email protected] (R.L.).
    More by Rafael Luque
Cite this: J. Phys. Chem. A 2020, 124, 10, 1911–1921
Publication Date (Web):February 13, 2020
https://doi.org/10.1021/acs.jpca.9b11157
Copyright © 2020 American Chemical Society

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    Abstract

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    UV photodecomposition of azidomethyl methyl sulfide (AMMS) yields a transient S-methylthiaziridine which rapidly evolves to S-methyl-N-sulfenylmethanimine at 10 K. This species was detected by infrared matrix isolation spectroscopy. The mechanism of the photoreaction of AMMS has been investigated by a combined approach, using low-temperature matrix isolation FTIR spectroscopy in conjunction with two theoretical methods, namely, complete active space self-consistent field and multiconfigurational second-order perturbation. The key step of the reaction is governed by a S2/S1 conical intersection localized in the neighborhood of the singlet nitrene minimum which is formed in the first reaction step of the photolysis, that is, N2 elimination from AMMS. Full assignment of the observed infrared spectra of AMMS has been carried out based on comparison with density functional theory and second-order perturbation Møller–Plesset methods.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jpca.9b11157.

    • Electronic spectra of AMMS and Hg lamp; PES for AMMS; experimental bands of AMMS trapped in the N2 matrix; atom numbering of geometries for vibrational analysis; set of internal coordinates defined for AMMS3, AMINA1, IMI1, and CH2NH; assignment of the calculated fundamental vibrational modes of AMMS3, cis and trans AMINA1, IMI1; FTIR matrix isolation spectrum of AMMS in Ar, N2 matrix after deposition, annealing; FTIR matrix spectrum of AMMS in Ar and Xe; SA-CASSCF/ANO-RCC orbitals in the active space of AMMS; CASSCF/ANO-RCC optimized geometries of the stationary points, minima of nitrene, and critical points; SA-CASSCF/ANO-RCC orbitals of singlet nitrene; CASSCF(14,11)-optimized geometrical parameters of AMMS; CASSCF(14e,13o)/ANO-RCC geometrical parameters of nitrene; and 1H-NMR spectra of AMMS using TMS as the reference (PDF)

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    Cited By

    This article is cited by 10 publications.

    1. Juanjuan Zhang, Jiawei Peng, Yifei Zhu, Deping Hu, Zhenggang Lan. Influence of Mode-Specific Excitation on the Nonadiabatic Dynamics of Methyl Nitrate (CH3ONO2). The Journal of Physical Chemistry Letters 2023, 14 (29) , 6542-6549. https://doi.org/10.1021/acs.jpclett.3c00664
    2. Juan Soto, Manuel Algarra. Electronic Structure of Nitrobenzene: A Benchmark Example of the Accuracy of the Multi-State CASPT2 Theory. The Journal of Physical Chemistry A 2021, 125 (43) , 9431-9437. https://doi.org/10.1021/acs.jpca.1c04595
    3. Marwa Louleb, Latifa Latrous, Ángel Ríos, Mohammed Zougagh, Enrique Rodríguez-Castellón, Manuel Algarra, Juan Soto. Detection of Dopamine in Human Fluids Using N-Doped Carbon Dots. ACS Applied Nano Materials 2020, 3 (8) , 8004-8011. https://doi.org/10.1021/acsanm.0c01461
    4. M. L. Birsa. Elimination Reactions. 2024, 281-293. https://doi.org/10.1002/9781119716846.ch8
    5. Sambit K. Das, Michael Odelius, Ambar Banerjee. Simulating Non‐Adiabatic Dynamics of Photoexcited Phenyl Azide: Investigating Electronic and Structural Relaxation en Route to the Formation of Phenyl Nitrene. Chemistry – A European Journal 2024, 30 (7) https://doi.org/10.1002/chem.202302178
    6. Meng-Kai Liu, Jian Li, Quan-Song Li, Ze-Sheng Li. Theoretical insights into photo-induced isomerization mechanisms of phenylsulfinyl radical PhSO˙. Physical Chemistry Chemical Physics 2022, 24 (10) , 6266-6273. https://doi.org/10.1039/D1CP05331K
    7. Juan Soto, Manuel Algarra, Daniel Peláez. Nitrene formation is the first step of the thermal and photochemical decomposition reactions of organic azides. Physical Chemistry Chemical Physics 2022, 24 (8) , 5109-5115. https://doi.org/10.1039/D1CP05785E
    8. Juan Soto, Daniel Peláez, Juan C. Otero. A SA-CASSCF and MS-CASPT2 study on the electronic structure of nitrosobenzene and its relation to its dissociation dynamics. The Journal of Chemical Physics 2021, 154 (4) https://doi.org/10.1063/5.0033181
    9. Jian Li, Meng-Kai Liu, Quan-Song Li, Ze-Sheng Li. Theoretical study on the photochemistry of furoylazides: Curtius rearrangement and subsequent reactions. Physical Chemistry Chemical Physics 2020, 22 (48) , 28317-28324. https://doi.org/10.1039/D0CP05539E
    10. Manuel Algarra, Juan Soto. Insights into the Thermal and Photochemical Reaction Mechanisms of Azidoacetonitrile. Spectroscopic and MS‐CASPT2 Calculations. ChemPhysChem 2020, 21 (11) , 1126-1133. https://doi.org/10.1002/cphc.202000201

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