Binuclear complex of the organogold derivative of nitronyl nitroxide with 1,1′-bis(diphenylphosphino)ferrocene: synthesis, structure, and properties

Binuclear complex of the organogold derivative of nitronyl nitroxide with 1,1′-bis(diphenylphosphino)ferrocene: synthesis, structure, and properties Full article

Journal

Russian Chemical Bulletin
ISSN: 1573-9171 , E-ISSN: 1066-5285

Output data

Year: 2024, Volume: 73, Number: 5, Pages: 1216-1228 Pages count : 13 DOI: 10.1007/s11172-024-4238-2

Authors

Zayakin I.A. ¹ , Syroeshkin M.A. ¹ , Shangin P.G. ¹ , Korlyukov A.A. ² , Dmitriev A.A. ³ , Gritsan N.P. ³ , Tretyakov E.V. ¹

Affiliations

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

A biradical formed by coordination of the organogold derivative of a nitronyl nitroxide radical with 1,1′-bis(diphenylphosphino)ferrocene was obtained. According to X-ray diffraction data, the Au—Au distance in the biradical structure is short (3.372 Å). The O atoms of paramagnetic groups form short intramolecular contacts with H atoms of cyclopentadienyl anions (2.360 and 2.581 Å) and with methyl H atoms (2.280 and 2.525 Å), as well as intermolecular contacts with H atoms of methyl groups (2.462 and 2.610 Å). Using cyclic voltammetry, it was established that the oxidation of the biradical occurs reversibly in three stages at potentials equal to −34, 232, and 845 mV vs. Ag/AgCl. Density functional calculations and the QTAIM and NBO analyses revealed that there is a weak noncovalent bond between gold atoms in the biradical complex due to partial transfer of an electron from the 5d orbital of one AuI ion to the 6s orbital of the other AuI ion. A weak intramolecular antiferromagnetic exchange interaction (J/kB ≈ −20 K) in the crystal structure was predicted.

Zayakin I.A. , Syroeshkin M.A. , Shangin P.G. , Korlyukov A.A. , Dmitriev A.A. , Gritsan N.P. , Tretyakov E.V.
Binuclear complex of the organogold derivative of nitronyl nitroxide with 1,1′-bis(diphenylphosphino)ferrocene: synthesis, structure, and properties
Russian Chemical Bulletin. 2024. V.73. N5. P.1216-1228. DOI: 10.1007/s11172-024-4238-2 WOS Scopus OpenAlex

Web of science:	WOS:001252371600031
Scopus:	2-s2.0-85196661708
OpenAlex:	W4399897768

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