A Phosphinonitronyl Nitroxide | Sciact

A Phosphinonitronyl Nitroxide Full article

Journal

ChemistrySelect
ISSN: 2365-6549

Output data

Year: 2025, Volume: 10, Number: 20, Article number : e01554, Pages count : DOI: 10.1002/slct.202501554

Authors

Zayakin Igor A. ¹ , Korlyukov Alexander A. ² , Syroeshkin Mikhail A. ¹ , Kadilenko Evgeny M. ³ , Gritsan Nina P. ³ , Tretyakov Evgeny V. ¹

Affiliations

1	N.D. Zelinsky Institute of Organic Chemistry Russian Academy of Sciences 47 Leninsky Ave. Moscow 119991 Russian Federation
2	A.N. Nesmeyanov Institute of Organoelement Compounds Russian Academy of Sciences 28 Vavilova Str. Moscow 119991 Russian Federation
3	V.V. Voevodsky Institute of Chemical Kinetics and Combustion Siberian Branch of Russian Academy of Sciences 3 Institutskaya Str. Novosibirsk 630090 Russian Federation

Nitronyl nitroxides are widely used in chemistry, physics, and materials science because of their inherently high reactivity and magnetic activity, but the synthesis of C(2)-organoelement derivatives is still a challenge. This paper describes effective synthesis and properties of the first nitronyl nitroxide carrying an additional redox-active phosphine group, namely 1,3,5,7-tetramethyl-8-(4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl-2-yl)-2,4,6-trioxa-8-phosphaadamantane. This phosphinonitronyl nitroxide was prepared by reacting lithiated nitronyl nitroxide with 8-bromo-1,3,5,7-tetramethyl-2,4,6-trioxa-8-phosphaadamantane. The paramagnet was characterized by cyclic voltammetry and electron spin resonance (ESR), infrared, and UV/vis spectroscopy supported by quantum chemical calculations. Molecular and crystal structure of the phosphinonitronyl nitroxide was established by X-ray structural analysis. ESR spectroscopy and density functional theory (DFT) calculations proved spin delocalization onto the phosphorus atom. According to the cyclic-voltammetry data, oxidation of the phosphinonitronyl nitroxide takes place quasi-reversibly at E1/2 = 0.76 V, and its reduction occurs chemically and electrochemically reversibly at E1/2 = −0.95 V (rel. Ag/AgCl).

Zayakin I.A. , Korlyukov A.A. , Syroeshkin M.A. , Kadilenko E.M. , Gritsan N.P. , Tretyakov E.V.
A Phosphinonitronyl Nitroxide
ChemistrySelect. 2025. V.10. N20. e01554 . DOI: 10.1002/slct.202501554 WOS OpenAlex

Web of science:	WOS:001492381600001
OpenAlex:	W4410556083

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