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Photochemical study on the reactivity of tetrasulfur tetranitride, S₄N₄

  • Pritchina, Elena A. Institute of Chemical Kinetics & Combustion, , Siberian Branch of the Russian Academy of Sciences, Novosibirsk, Russia, - Department of Natural Sciences and Department of Physics, Novosibirsk State University, Novosibirsk, Russia, and
  • Gritsan, Nina P. Institute of Chemical Kinetics & Combustion, , Siberian Branch of the Russian Academy of Sciences, Novosibirsk, Russia, - Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences, Novosibirsk, Russia
  • Zibarev, Andrey V. Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences, Novosibirsk, Russia
  • Bally, Thomas Department of Chemistry, University of Fribourg, Switzerland
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    01.04.2009
Published in:
  • Inorganic Chemistry. - 2009, vol. 48, no. 9, p. 4075–4082
English To elucidate the multifaceted but poorly understood chemistry of the pivotal polysulfur−nitrogen heterocycle, tetrasulfur tetranitride (S₄N₄, 1), its photochemistry was studied in Ar matrices. Thereby two primary intermediates and a secondary one (24) were detected, and their UV−vis and IR spectra were identified through specific interconversions of 14 that can be induced by selective irradiations. The structures associated with these spectra were assigned with the help of DFT calculations. From these assignments it follows that, under the conditions of the present experiments, the cage structure of 1 transforms into isomeric structures 24, one of which is a boat-shaped 8-membered cycle (2), and the two other are novel 6-membered S₃N₃ cycles carrying exocyclic (N)SN (3) or (S)N=S (4) groups, respectively, which have not been previously described. These three intermediates probably play a pivotal role in the formation of the diverse products that are observed in the reactions of S₄N₄ even under mild reaction conditions.
Faculty
Faculté des sciences et de médecine
Department
Département de Chimie
Language
  • English
Classification
Chemistry
License
License undefined
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Persistent URL
https://folia.unifr.ch/unifr/documents/301374
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