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Ferrocene-containing Schiff bases and their Sn( iv ) complexes with two non-conjugated redox-active fragments: dependence of spectroscopic and redox properties on complexation and solvent Научная публикация

Журнал New Journal of Chemistry
ISSN: 1369-9261 , E-ISSN: 1144-0546
Вых. Данные Год: 2026, DOI: 10.1039/d5nj04462f
Авторы Proshutinskaya Varvara Yu. 1 , Krylova Irina V. 1 , Shangin Pavel G. 1 , Vilman Victoriya A. 1 , Minyaev Mikhail E. 1 , Gorbunov Dmitry E. 2 , Gritsan Nina P. 2 , Nikolaevskaya Elena N. 1 , Egorov Mikhail P. 1 , Tretyakov Evgeny V. 1 , Syroeshkin Mikhail A. 1
Организации
1 N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 119991 Moscow, Russia
2 V.V. Voevodsky Institute of Chemical Kinetics and Combustion, Siberian Branch of Russian Academy of Sciences, 630090 Novosibirsk, Russia

Реферат: In this study, ligands and tin(IV) complexes containing two non-conjugated redox-active fragments—a Schiff base and an imino-substituted ferrocene—were synthesized and characterized using techniques, including X-ray diffraction analysis. Complexation with tin(IV) was found to induce a dramatic increase (approximately 50-fold) in absorption intensity within the visible region. In the solid state, the complexes adopt a dimeric structure stabilized by Sn–O coordination bonds between adjacent molecules. Notably, a significant proportion of the corresponding dimer persists even in highly diluted solutions, irrespective of solvent polarity. The redox properties of the synthesized compounds were investigated in aprotic media (DMF and MeCN). Reduction processes in both ligands and their tin(IV) complexes involve the Schiff-base moiety, as anticipated, given the redox inertness of ferrocene at negative potentials. In contrast, electrochemical oxidation exhibits greater complexity, with both redox-active components—the Schiff base and ferrocene. The oxidation of ligands is chemically reversible, confirming that the ferrocene unit serves as the primary redox center. In turn, the oxidation of complexes (first stage) is chemically irreversible, proceeding via the Schiff-base moiety of the monomer. The monomeric cation radicals formed during the initial oxidation undergo rapid dimerization. The resulting dimers are further oxidized at more positive potentials, producing a reversible wave attributable to electron transfer from the ferrocene units. Density functional theory (DFT) calculations corroborate these findings, confirming electron transfer from the ferrocene moiety during ligand oxidation and electron transfer from the Schiff base during oxidation of the monomeric complexes.
Библиографическая ссылка: Proshutinskaya V.Y. , Krylova I.V. , Shangin P.G. , Vilman V.A. , Minyaev M.E. , Gorbunov D.E. , Gritsan N.P. , Nikolaevskaya E.N. , Egorov M.P. , Tretyakov E.V. , Syroeshkin M.A.
Ferrocene-containing Schiff bases and their Sn( iv ) complexes with two non-conjugated redox-active fragments: dependence of spectroscopic and redox properties on complexation and solvent
New Journal of Chemistry. 2026. DOI: 10.1039/d5nj04462f WOS Scopus OpenAlex
Даты:
Поступила в редакцию: 14 нояб. 2025 г.
Опубликована online: 2 февр. 2026 г.
Идентификаторы БД:
Web of science: WOS:001688833400001
Scopus: 2-s2.0-105030292773
OpenAlex: W7127099522
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