Redox behavior of the Fe(IV) cage complex with 1,4,7-triazacyclononane (tacn) and formaldoxime trimer (tfo) ([FeIV(tacn)(tfo)]+Cl–) in dimethylformamide and acetonitrile solutions

Redox behavior of the Fe(IV) cage complex with 1,4,7-triazacyclononane (tacn) and formaldoxime trimer (tfo) ([FeIV(tacn)(tfo)]+Cl–) in dimethylformamide and acetonitrile solutions Научная публикация

Журнал

Electrochimica Acta
ISSN: 1873-3859 , E-ISSN: 0013-4686

Вых. Данные

Год: 2026, Номер статьи : 150389, Страниц : DOI: 10.1016/j.electacta.2026.150389

Авторы

Babiy Anton O. ^1,2 , Kuznetsov Vitaly V. ³ , Korotenko Vasilii N. ⁴ , Sukhorukov Alexey Yu. ⁵ , Golovanov Ivan S. ⁵ , German Konstantin E. ³ , Pirogov Andrey V. ⁶ , Bolotnik Timofey A. ⁶ , Frolov Kirill V. ⁷

Организации

1	Bauman Moscow State Technical University, Moscow, 105005, Russian Federation
2	D.I. Mendeleev University of Chemical Technology of Russia, Moscow, 125047, Russian Federation
3	Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Moscow 119071, Russian Federation
4	Institute of Thermal Separation Processes, Hamburg University of Technology (TUHH), 21073, Hamburg, Germany
5	Laboratory of Organic and Metal−Organic Nitrogen−Oxygen Systems (LOMONOS), N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, 119991, Russian Federation
6	Lomonosov Moscow State University, Moscow, 119991, Russian Federation
7	Shubnikov Institute of Crystallography, Kurchatov Complex of Crystallography and Photonics, National Research Center Kurchatov Institute, Moscow, 119333 Russian Federation

The redox behavior of the [FeIV(tacn)(tfo)]+ cage cation was studied by cyclic voltammetry. The complex is electrochemically active in both the cathodic and anodic potential regions. The products of electrochemical transformations were characterized using a combination of physicochemical methods, including UV-Vis absorbance spectrometry, GC/MS analysis of the vapor phase over the solution, Mössbauer spectrometry, and X-ray photoelectron spectroscopy (XPS). Reduction of [FeIV(tacn)(tfo)]+ in dimethylformamide (DMF) results in dimethylamine formation. Fe(IV) remains the predominant iron oxidation state after electrolysis, while Mössbauer spectroscopy reveals a significant Fe(III) fraction, consistent with the formation of a reactive Fe(III) intermediate. In contrast, in acetonitrile (MeCN), reduction of [FeIV(tacn)(tfo)]+ results in decomposition of the coordination complex, formation of ligand-derived species, and finally deposition of metallic iron on the cathode at sufficiently negative electrode potentials. An anodic redox process assigned to the FeIV/FeV couple is observed in both solvents; however, this process is substantially more reversible in MeCN than in DMF. The causes of the different redox behavior of [FeIV(tacn)(tfo)]+ in DMF and acetonitrile and possible reaction pathways are discussed.

Babiy A.O. , Kuznetsov V.V. , Korotenko V.N. , Sukhorukov A.Y. , Golovanov I.S. , German K.E. , Pirogov A.V. , Bolotnik T.A. , Frolov K.V.
Redox behavior of the Fe(IV) cage complex with 1,4,7-triazacyclononane (tacn) and formaldoxime trimer (tfo) ([FeIV(tacn)(tfo)]+Cl–) in dimethylformamide and acetonitrile solutions
Electrochimica Acta. 2026. 150389 . DOI: 10.1016/j.electacta.2026.150389

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