Abstract: 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.

Cite: 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 OpenAlex

Dates:

Published print:

Apr 1, 2018

Identifiers:

Web of science:	WOS:000430028400025
Scopus:	2-s2.0-85042936657
Elibrary:	35507548
OpenAlex:	W2791023106

Citing:

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Web of science	10
Scopus	8
Elibrary	13
OpenAlex	11

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