Fused 1,2,3-Thiaselenazoles Synthesized from 1,2,3-Dithiazoles through Selective Chalcogen Exchange

Fused 1,2,3-Thiaselenazoles Synthesized from 1,2,3-Dithiazoles through Selective Chalcogen Exchange Full article

Journal

Chemistry - A European Journal
ISSN: 0947-6539 , E-ISSN: 1521-3765

Output data

Year: 2017, Volume: 23, Number: 67, Pages: 17037-17047 Pages count : 11 DOI: 10.1002/chem.201703182

Tags

density functional calculations; dithiazoles; synthetic methods; thiaselenazoles; X-ray diffraction

Authors

Konstantinova Lidia S. ^1,2 , Baranovsky Ilia V. ¹ , Pritchina Elena A. ^3,4 , Mikhailov Maksim S. ² , Bagryanskaya Irina Yu. ^4,5 , Semenov Nikolay A. ⁵ , Irtegova Irina G. ⁵ , Salnikov Georgy E. ^4,5 , Lyssenko Konstantin A. ⁶ , Gritsan Nina P. ^3,7 , Zibarev Andrey V. ^5,7,8 , Rakitin Oleg A. ^1,2

Affiliations

1	(Данные Web of science) Russian Acad Sci, Inst Organ Chem, Moscow 119991, Russia
2	(Данные Web of science) South Ural State Univ, Nanotechnol Educ & Res Ctr, Chelyabinsk 454080, Russia
3	(Данные Web of science) Russian Acad Sci, Inst Chem Kinet & Combust, Siberian Branch, Novosibirsk 630090, Russia
4	(Данные Web of science) Novosibirsk State Univ, Dept Nat Sci, Novosibirsk 630090, Russia
5	(Данные Web of science) Russian Acad Sci, Inst Organ Chem, Siberian Branch, Novosibirsk 630090, Russia
6	(Данные Web of science) Russian Acad Sci, Inst Organoelement Cpds, Moscow 119991, Russia
7	(Данные Web of science) Novosibirsk State Univ, Dept Phys, Novosibirsk 630090, Russia
8	(Данные Web of science) Tomsk State Univ, Dept Chem, Tomsk 634050, Russia

A new approach to the synthesis of fused 1,2,3-thiaselenazolesrare five-membered heterocycles that contain two different chalcogensfrom the corresponding 1,2,3-dithiazoles and SeO2 was accomplished by selective exchange of S and Se atoms. The fused carbo- and heterocyclic units were indene, naphthalenone, cyclohexadienone, cyclopentadiene, benzoannulene, and benzoxazine. The molecular structures of two of the thiaselenadiazole products and one of the dithiazole precursors were confirmed by single-crystal X-ray diffraction. The reaction is highly solvent selective; it only takes place in solvents that contain a C=O group (e.g., DMF or tetramethylurea). According to DFT calculations, the reaction is thermodynamically favorable. Based on the DFT calculations and (SeNMR)-Se-77 spectroscopy, two tentative mechanisms that feature isomeric transition states and intermediates are suggested for the reaction via ring-opening addition of SeO2 to the S-X dithiazole bond (X=N or S). The DFT-calculated first adiabatic electron affinities of the compounds were chalcogen independent and positive in all cases, which assumes formation of thermodynamically stable radical anions (RAs). These calculated RAs featured either normal or abnormal elongation of the S1-X2 (X=S or Se) bond relative to their neutral precursors and possessed * or sigma* SOMOs, respectively.

Konstantinova L.S. , Baranovsky I.V. , Pritchina E.A. , Mikhailov M.S. , Bagryanskaya I.Y. , Semenov N.A. , Irtegova I.G. , Salnikov G.E. , Lyssenko K.A. , Gritsan N.P. , Zibarev A.V. , Rakitin O.A.
Fused 1,2,3-Thiaselenazoles Synthesized from 1,2,3-Dithiazoles through Selective Chalcogen Exchange
Chemistry - A European Journal. 2017. V.23. N67. P.17037-17047. DOI: 10.1002/chem.201703182 WOS Scopus РИНЦ OpenAlex

Published online:	Nov 8, 2017
Published print:	Dec 1, 2017

Web of science:	WOS:000418570000019
Scopus:	2-s2.0-85034055502
Elibrary:	35505425
OpenAlex:	W2753807218

DB	Citing
Web of science	19
Scopus	21
OpenAlex	23