1,3-Diaza[3]ferrocenophanes functionalized with a nitronyl nitroxide group

1,3-Diaza[3]ferrocenophanes functionalized with a nitronyl nitroxide group Full article

Journal

Tetrahedron
ISSN: 0040-4020

Output data

Year: 2018, Volume: 74, Number: 15, Pages: 1942-1950 Pages count : 9 DOI: 10.1016/j.tet.2018.02.062

Tags

Iminophosphoranes; Arylisocyanates; aza-Wittig reaction; Phosphonium betaines; 1,3-Diaza[3]ferrocenophane; Nitronyl nitroxides; Monocrystal XRD

Authors

Gurskaya Larisa ¹ , Bagryanskaya Irina ^1,2 , Amosov Evgeny ¹ , Kazantsev Maxim ^1,2 , Politanskaya Larisa ¹ , Zaytseva Elena ¹ , Bagryanskaya Elena ^1,2 , Chernonosov Aleksander ³ , Tretyakov Evgeny ^1,2

Affiliations

1	(Данные Web of science) NN Vorozhtsov Novosibirsk Inst Organ Chem, 9 Ac Lavrentiev Ave, Novosibirsk 630090, Russia
2	(Данные Web of science) Novosibirsk State Univ, Natl Res Univ, Novosibirsk 630090, Russia
3	(Данные Web of science) Inst Chem Biol & Fundamental Med, 8 Ac Lavrentiev Ave, Novosibirsk 630090, Russia

An aza-Wittig reaction of 1,1'-bis(triphenylphosphoranylidenamino)-ferrocene with 4-iodo-, 2,5-difluoro-4-iodo-, pentafluoro-, or 4-methoxycarbonylphenylisocyanates is described here. Intermediate betaines, which are products of a nucleophilic attack of the nitrogen atom of the remaining iminophosphorane moiety on the carbon atom of the carbodiimide functional group, were isolated; their structures were proved by monocrystal X-ray diffraction. Hydrolysis of the betaines under mild conditions gave corresponding arylamino-1,3-diaza[3]ferrocenophanes. On the other hand, as demonstrated, under more rigid conditions, the betaines could be converted into ferrocenophanes with the 1,3-diazetidine-2,4-diimine coupler. The iodo- or diiodo-derivatives of 1,3-diaza[3]ferrocenophanes were cross-coupled with a nitronyl nitroxide-2-ide gold(l) complex to obtain corresponding metallocenophanes functionalized with the nitronyl nitroxide group(s). The molecular and crystal structures of the halogenated and spin-labeled ferrocenophanes were solved by X-ray analysis. In arylamino-1,3-diaza[3]ferrocenophanes, according to cyclic voltammetry, the position of the quasi-reversible oxidation peak associated with the Fe(II)/Fe(III) redox couple deviates within 0.09 V depending on substituents in the arylamino group. (C) 2018 Elsevier Ltd. All rights reserved.

Gurskaya L. , Bagryanskaya I. , Amosov E. , Kazantsev M. , Politanskaya L. , Zaytseva E. , Bagryanskaya E. , Chernonosov A. , Tretyakov E.
1,3-Diaza[3]ferrocenophanes functionalized with a nitronyl nitroxide group
Tetrahedron. 2018. V.74. N15. P.1942-1950. DOI: 10.1016/j.tet.2018.02.062 WOS Scopus РИНЦ

Published print:

Apr 1, 2018

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