TY - JOUR

T1 - Synthesis, structural peculiarities, and photosensitivity of fluorinated dibenzo-1,2,5,6-tetrathiocines

AU - Buravlev, Alexander A.

AU - Makarov, Alexander Yu

AU - Salnikov, Georgy E.

AU - Genaev, Alexander M.

AU - Bagryanskaya, Irina Yu

AU - Nikulshin, Pavel V.

AU - Platonov, Vyacheslav E.

AU - Zibarev, Andrey V.

N1 - The authors are grateful to Prof. Tatiana V. Mezhenkova for generous gift of decafluoro indane, and to the Russian Science Foundation (RSF) and Government of the Novosibirsk region (GNR) for joint financial support of this work (RSF-GNR project no. 24-23-20101). The Multi-Access Chemical Research Centre (Institute of Organic Chemistry) and Information Computation Centre (Novosibirsk State University) are gratefully acknowledged for instrumental and computational facilities, respectively.

PY - 2024/7/1

Y1 - 2024/7/1

N2 - 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 C2 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. © 2024 The Royal Society of Chemistry.

AB - 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 C2 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. © 2024 The Royal Society of Chemistry.

UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-85197511617&origin=inward&txGid=52f76fa6b3ca7521f50726d8e25ed146

UR - https://www.mendeley.com/catalogue/83db5c48-9b02-31ed-853d-38d29091f890/

U2 - 10.1039/d4nj02284j

DO - 10.1039/d4nj02284j

M3 - Article

VL - 48

SP - 12807

EP - 12816

JO - New Journal of Chemistry

JF - New Journal of Chemistry

SN - 1144-0546

IS - 28

ER -