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

Larisa Gurskaya, Irina Bagryanskaya, Evgeny Amosov, Maxim Kazantsev, Larisa Politanskaya, Elena Zaytseva, Elena Bagryanskaya, Aleksander Chernonosov, Evgeny Tretyakov

Research output: Contribution to journalArticlepeer-review

3 Citations (Scopus)

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(I) 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.

Original languageEnglish
Pages (from-to)1942-1950
Number of pages9
JournalTetrahedron
Volume74
Issue number15
DOIs
Publication statusPublished - 12 Apr 2018

Keywords

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

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