TY - JOUR

T1 - 1,3-Diaza[3]ferrocenophanes functionalized with a nitronyl nitroxide group

AU - Gurskaya, Larisa

AU - Bagryanskaya, Irina

AU - Amosov, Evgeny

AU - Kazantsev, Maxim

AU - Politanskaya, Larisa

AU - Zaytseva, Elena

AU - Bagryanskaya, Elena

AU - Chernonosov, Aleksander

AU - Tretyakov, Evgeny

N1 - Funding Information: The authors thank the Russian Foundation for Basic Research (project # 15-03-01850 ) for financial support. This work has been supported by the Russian Ministry of Science and Education under the 5-100 Excellence Program. The Multi-Access Center of the Novosibirsk Institute of Organic Chemistry of SB RAS is acknowledged too. Publisher Copyright: © 2018 Elsevier Ltd

PY - 2018/4/12

Y1 - 2018/4/12

N2 - 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.

AB - 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.

KW - 1,3-Diaza[3]ferrocenophane

KW - Arylisocyanates

KW - Aza-Wittig reaction

KW - Iminophosphoranes

KW - Monocrystal XRD

KW - Nitronyl nitroxides

KW - Phosphonium betaines

KW - aza-Wittig reaction

UR - http://www.scopus.com/inward/record.url?scp=85042936657&partnerID=8YFLogxK

U2 - 10.1016/j.tet.2018.02.062

DO - 10.1016/j.tet.2018.02.062

M3 - Article

AN - SCOPUS:85042936657

VL - 74

SP - 1942

EP - 1950

JO - Tetrahedron

JF - Tetrahedron

SN - 0040-4020

IS - 15

ER -