Fluorinated Organic Paramagnetic Building Blocks for Cross-Coupling Reactions

Fluorinated Organic Paramagnetic Building Blocks for Cross-Coupling Reactions Full article

Journal

Molecules
, E-ISSN: 1420-3049

Output data

Year: 2020, Volume: 25, Number: 22, Article number : 427, Pages count : DOI: 10.3390/molecules25225427

Tags

aromatic nucleophilic substitution; fluoroarenes; functionalized nitroxides; stable organic radicals; tert-butylarylnitroxides

Authors

Politanskaya L.V. ¹ , Fedyushin P.A. ¹ , Rybalova T.V. ¹ , Bogomyakov A.S. ² , Asanbaeva N.B. ¹ , Tretyakov E.V. ^1,3

Affiliations

1	(Scopus) N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, 9 Ac. Lavrentiev Avenue, Novosibirsk, 630090, Russian Federation
2	(Scopus) International Tomography Center, Siberian Branch of Russian Academy of Sciences, 3a Institutskaya Str., Novosibirsk, 630090, Russian Federation
3	(Scopus) N.D. Zelinsky Institute of Organic Chemistry, Leninsky Prospect ,47Moscow 119991, Russian Federation

New stable polyfluorinated nitroxide radicals for use in cross-coupling reactions, namely, N-tert-butyl-N-oxyamino-2,3,5,6-tetrafluoro-4-iodobenzene and N-tert-butyl-N-oxyamino-2,3,5,6-tetrafluoro-4-ethynylbenzene, were prepared from perfluoroiodobenzene. The reaction of the polyfluoro derivative with tert-butylamine under autoclaving conditions leading to the formation of N-tert-butyl-2,3,5,6-tetrafluoro-4-iodoaniline proved to be the key stage of the whole process. The fluorinated tert-butyl iodophenyl nitroxide was found to form in a solid state via N-O···I halogen bonds, a one-dimensional assembly of the radicals. The acceptor role of the nitroxide group in the halogen bonding changes to a donor role when the nitroxide reacts with Cu(hfac)2. In the last case, zero-dimensional assembly prevails, giving a three-spin complex with axial coordinated nitroxide groups and, as a consequence, causing ferromagnetic intramolecular exchange interactions between Cu(II) and radical spins.

Politanskaya L.V. , Fedyushin P.A. , Rybalova T.V. , Bogomyakov A.S. , Asanbaeva N.B. , Tretyakov E.V.
Fluorinated Organic Paramagnetic Building Blocks for Cross-Coupling Reactions

Molecules. 2020. V.25. N22. 427 . DOI: 10.3390/molecules25225427 WOS Scopus РИНЦ

Full text from publisher

Published online:

Nov 19, 2020

Web of science	WOS:000594125000001
Scopus	2-s2.0-85096734850
Elibrary	45122791
OpenAlex	W3103859812