Aromatic S-N(F)-Approach to Fluorinated Phenyl tert-Butyl Nitroxides

Aromatic S-N(F)-Approach to Fluorinated Phenyl tert-Butyl Nitroxides Full article

Journal

Molecules
, E-ISSN: 1420-3049

Output data

Year: 2019, Volume: 24, Number: 24, Article number : 4493, Pages count : DOI: 10.3390/molecules24244493

Tags

fluoroarenes; aromatic nucleophilic substitution; tert-butylanilines; nitroxides; copper-nitroxide complexes; magneto-structural correlations

Authors

Tretyakov Evgeny ^1,2 , Fedyushin Pavel ¹ , Panteleeva Elena ^1,2 , Gurskaya Larisa ¹ , Rybalova Tatyana ^1,2 , Bogomyakov Artem ^2,3 , Zaytseva Elena ^1,2 , Kazantsev Maxim ¹ , Shundrina Inna ^1,2 , Ovcharenko Victor ³

Affiliations

1	(Данные Web of science) NN Vorozhtsov Inst Organ Chem, 9 Ac Lavrentiev Ave, Novosibirsk 630090, Russia
2	(Данные Web of science) Novosibirsk State Univ, 2 Pirogova Str, Novosibirsk 630090, Russia
3	(Данные Web of science) Int Tomog Ctr, 3a Inst Skaya Str, Novosibirsk 630090, Russia

The interaction of octafluorotoluene (1a), as well as pentafluorobenzonitrile (1b) with tert-butylamine, followed by the oxidation of thus formed tert-butylanilines (2a,b) with meta-chloroperoxybenzoic acid led to functionalized perfluorinated phenyl tert-butyl nitroxides [namely, 4-(N-tert-butyl(oxyl)amino)heptafluorotoluene (3a) and 4-(N-tert-butyl(oxyl)amino)tetrafluorobenzonitrile (3b)] with nearly quantitative total yields. The molecular and crystal structures of nitroxide 3a were proved by single crystal X-ray diffraction analysis. The radical nature of both nitroxides was confirmed by ESR data. The interaction of Cu(hfac)(2) with the obtained nitroxides 3a,b gave corresponding trans-bis(1,1,1,5,5,5-hexafluoropentane-2,4-dionato-kappa O-2,O')bis{4-(N-tert-butyl(oxyl)amino)perfluoroarene-kappa O}copper (II) complexes ([Cu(hfac)(2)(3a)(2)] and [Cu(hfac)(2)(3b)(2)]). X-ray crystal structure analysis showed square bipyramid coordination of a centrally symmetric Cu polyhedron with the axial positions occupied by oxygen atoms of the nitroxide groups. Magnetic measurements revealed intramolecular ferromagnetic exchange interactions between unpaired electrons of Cu(II) ions and paramagnetic ligands, with exchange interaction parameters J(Cu-R) reaching 53 cm(-1).

Tretyakov E. , Fedyushin P. , Panteleeva E. , Gurskaya L. , Rybalova T. , Bogomyakov A. , Zaytseva E. , Kazantsev M. , Shundrina I. , Ovcharenko V.
Aromatic S-N(F)-Approach to Fluorinated Phenyl tert-Butyl Nitroxides

Molecules. 2019. V.24. N24. 4493 . DOI: 10.3390/molecules24244493 WOS Scopus РИНЦ

Full text from publisher

Published online:

Dec 8, 2019

Web of science	WOS:000507299600071
Scopus	2-s2.0-85076381618
Elibrary	43221031
OpenAlex	W2993098256