Reaction of Paramagnetic Synthon, Lithiated 4,4,5,5‐Tetramethyl‐4,5‐dihydro‐1H‐imidazol‐1‐oxyl 3‐oxide, with Cyclic Aldonitrones of the Imidazole Series

Reaction of Paramagnetic Synthon, Lithiated 4,4,5,5‐Tetramethyl‐4,5‐dihydro‐1H‐imidazol‐1‐oxyl 3‐oxide, with Cyclic Aldonitrones of the Imidazole Series Научная публикация

Журнал

Chemistry - A European Journal
ISSN: 0947-6539

Вых. Данные

Год: 2016, Том: 22, Номер: 41, Страницы: 14598-14604 Страниц : 7 DOI: 10.1002/chem.201602049

Авторы

Tolstikov Svyatoslav E. ¹ , Tretyakov Evgeny V. ^2,3 , Gorbunov Dmitry E. ^3,4 , Zhurko Irina F. ^2,3 , Fedin Matvey V. ^1,3 , Romanenko Galina V. ¹ , Bogomyakov Artem S. ¹ , Gritsan Nina P. ^3,4 , Mazhukin Dmitry G. ^2,3

Организации

1	International Tomography Center, 3a Institutskaya Str., Novosibirsk, 630090 Russia
2	N. N. Vorozhtsov Institute of Organic Chemistry, 9 Ac. Lavrentiev Avenue, Novosibirsk, 630090 Russia
3	Novosibirsk State University, 2 Pirogova Str., Novosibirsk, 630090 Russia
4	V. V. Voevodsky Institute of Chemical Kinetics and Combustion, 3 Institutskaya Str., Novosibirsk, 630090 Russia

It was shown that dipole-stabilized paramagnetic carbanion lithiated 4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-1-oxyl 3-oxide can be attached in a nucleophilic manner to either isolated or conjugated aldonitrones of the 2,5-dihydroimidazole 3-oxide and 2H-imidazole 1-oxide series to afford adducts the subsequent oxidation of which leads to polyfunctional mono- and diradicals. According to XRD, at least two polymorphic modifications can be formed during crystallization of the resulting paramagnetic compounds, and for each of them, geometric parameters of the molecules are similar. An EPR spectrum of the diradical in frozen toluene has a complicated lineshape, which can be fairly well reproduced by using X-ray diffraction structural analysis and the following set of parameters: D=14.9 mT, E=1.7 mT; tensor a(14N)=[0.260 0.260 1.625] mT, two equivalent tensors for the nitronyl nitroxide moiety a(14N)=[0.198 0.198 0.700] mT, and g≈2.007. According to our DFT and ab initio calculations, the intramolecular exchange in the diradical is very weak and most likely ferromagnetic.

Tolstikov S.E. , Tretyakov E.V. , Gorbunov D.E. , Zhurko I.F. , Fedin M.V. , Romanenko G.V. , Bogomyakov A.S. , Gritsan N.P. , Mazhukin D.G.
Reaction of Paramagnetic Synthon, Lithiated 4,4,5,5‐Tetramethyl‐4,5‐dihydro‐1H‐imidazol‐1‐oxyl 3‐oxide, with Cyclic Aldonitrones of the Imidazole Series
Chemistry - A European Journal. 2016. V.22. N41. P.14598-14604. DOI: 10.1002/chem.201602049 WOS Scopus

Опубликована online:	19 авг. 2016 г.
Опубликована в печати:	4 окт. 2016 г.

Web of science:	WOS:000384698500027
Scopus:	2-s2.0-84982242933

БД	Цитирований
Scopus	22
Web of science	20