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 , E-ISSN: 1521-3765

Вых. Данные

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

Ключевые слова

ab initio calculations; density functional calculations; diradicals; EPR spectroscopy; X-ray diffraction

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	(Данные Web of science) Int Tomog Ctr, 3a Inst Skaya Str, Novosibirsk 630090, Russia
2	(Данные Web of science) NN Vorozhtsov Inst Organ Chem, 9 Ac Lavrentiev Ave, Novosibirsk 630090, Russia
3	(Данные Web of science) Novosibirsk State Univ, 2 Pirogova Str, Novosibirsk 630090, Russia
4	(Данные Web of science) VV Voevodsky Inst Chem Kinet & Combust, 3 Inst Skaya 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=14.9mT, E=1.7mT; tensor a(N-14)=[0.260 0.260 1.625] mT, two equivalent tensors for the nitronyl nitroxide moiety a(N-14)=[0.198 0.198 0.700] mT, and g approximate to 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 РИНЦ

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

Web of science	WOS:000384698500027
Scopus	2-s2.0-84982242933
РИНЦ	29464809
OpenAlex	W2515177807