На сайте журнала New Journal of Chemistry(IF 2,7) опубликована статья сотрудников Института:
Synthesis, structural peculiarities, and photosensitivity of fluorinated dibenzo-1,2,5,6-tetrathiocines
Alexander Andreevich Buravlev, Alexander Makarov, Georgy E. Salnikov, Alexander Genaev, Irina Yu. Bagryanskaya, Pavel Viktorovich Nikulshin, Vyacheslav E. Platonov and Andrey Viktorovich Zibarev
New J. Chem., 2024,
Published: 01 Jul 2024
doi: 10.1039/D4NJ02284J
Abstract
New fluorinated dibenzo-1,2,5,6-tetrathiocines 1 and 2 were synthesized by a novel condensation of 1,2-disulfenyl chlorides under the influence of elemental Cu, and structurally defined in the solid state, solution, and gas phase by single-crystal XRD, variable-temperature 19F NMR and NOESY, and DFT calculations. Crystalline 1 and 2 exhibited the C2h chair and С2 twist molecular conformations, respectively. Unlike 1 displayed only C…S shortened intermolecular contacts, crystal structure of 2 featured F…π, F...F, F…S and S...S contacts. In toluene solutions at 296 K, both twist and chair conformers were observed in the ~1:1 and ~7:1 ratios for 1 and 2, respectively. For 1, the twist ↔ chair conformer interconversion was practically temperature-independent, and for 2 revealed ΔH ~3.5 kJ mol–1 and ΔS ~4.4 J K–1 mol–1. With DFT, the PESs for twist-chair transformation and twist-twist racemization were analyzed and the TSs exhibiting twist-halfchair and boat conformations, respectively, were found. Several additional stationary points on the PESs, corresponding to hidden intermediates and bifurcation points and featuring twistboat and halfchair conformations were detected. In chloroform solution under sunlight, 1 underwent 1,2,5,6-tetrathiocine → 1,2,3,6-tetrathiocine isomerization whose product was characterized by XRD.
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