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

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. © 2020 American Chemical Society.

Algarra M.1 , Soto J.2 , Pinto Da Silva L. , Pino-González M.S.5 , Rodríguez-Borges J.E.3 , Mascetti J.6 , Borget F.7 , Reisi-Vanani A.8 , Luque R. 9, 10
American Chemical Society
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  • 1 CQM-Centro de Química da Madeira, Universidade da Madeira, Campus Universitário da Penteada, Funchal, 9020-105, Portugal
  • 2 Department Physical Chemistry, Faculty of Science, University Málaga, Málaga, 29016, Spain
  • 3 Chemistry Research Unit (CIQUP), Department of Chemistry and Biochemistry, Faculty of Sciences, University of Porto, R. Campo Alegre 697, Porto, 4169-007, Portugal
  • 4 LACOMEPHI, GreenUP, Department of Geosciences, Environment and Territorial Planning, Faculty of Sciences, University of Porto, R. Campo Alegre 697, Porto, 4169-007, Portugal
  • 5 Department Organic Chemistry, Faculty of Science, University Málaga, Málaga, 29016, Spain
  • 6 Institut des Sciences Moléculaires, University Bordeaux, Talence, 33405, France
  • 7 Physique des Interactions Ioniques et Moléculaires, Aix Marseille University, Marseille, 13007, France
  • 8 Department of Physical Chemistry, Faculty of Chemistry, University of Kashan, Kashan, 87317-51167, Iran
  • 9 Department Organic Chemistry, University Córdoba, Edif. Marie Curie, Ctra N IVa Km 396, Córdoba, 14014, Spain
  • 10 Peoples Friendship University of Russia, RUDN University, 6 Miklukho Maklaya str., Moscow, 117198, Russian Federation
Ключевые слова
Fourier transform infrared spectroscopy; Photolysis; Potential energy; Quantum chemistry; Sulfur compounds; Temperature; Complete active space self consistent fields; Conical intersection; Infrared matrix isolation; Infrared spectrum; Low temperature matrices; Photo-decomposition; Second order perturbation; Theoretical methods; Density functional theory
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