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Photochemical Study on the Reactivity of Tetrasulfur Tetranitride, S4N4

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journal contribution
posted on 04.05.2009 by Elena A. Pritchina, Nina P. Gritsan, Andrey V. Zibarev, Thomas Bally
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)SN (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.