Iron(iv) complexes with tetraazaadamantane-based ligands: synthesis, structure, applications in dioxygen activation and labeling of biomolecules

Iron(iv) complexes with tetraazaadamantane-based ligands: synthesis, structure, applications in dioxygen activation and labeling of biomolecules Full article

Journal

Dalton Transactions
ISSN: 1477-9234 , E-ISSN: 1477-9226

Output data

Year: 2022, Volume: 51, Number: 11, Pages: 4284-4296 Pages count : 13 DOI: 10.1039/d1dt04104e

Authors

Golovanov Ivan S. ¹ , Leonov Anton V. ^2,1 , Lesnikov Vladislav K. ¹ , Pospelov Evgeny V. ^2,1 , Frolov Kirill V. ³ , Korlyukov Alexander A. ⁴ , Nelyubina Yulia V. ⁴ , Novikov Valentin V. ⁴ , Sukhorukov Alexey Yu. ^5,1,6

Affiliations

1	N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky prospect, 47, Moscow, Russia
2	M. V. Lomonosov Moscow State University, Leninskiye Gory, 1, Moscow, Russia
3	Shubnikov Institute of Crystallography of FSRC “Crystallography and Photonics”, Russian Academy of Sciences, Leninsky prospect, 59, Moscow, 119333, Russia
4	A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov str. 28, Moscow, Russia
5	Plekhanov Russian University of Economics, Stremyanny per. 36, Moscow, Russia
6	D. Mendeleev University of Chemical Technology of Russia, Miusskaya sq. 9, Moscow, Russia

4,6,10-Trihydroxy-1,4,6,10-tetraazaadamantane (TAAD) has been shown to form a stable Fe(IV) complex having a diamantane cage structure, in which the metal center is coordinated by three oxygen atoms of the deprotonated ligand. The complex was characterized by X-ray diffraction analysis, HRMS, NMR, FT-IR, Mössbauer spectroscopy and DFT calculations, which supported the d4 configuration of iron. The Fe(IV)-TAAD complex showed excellent performance in dioxygen activation under mild conditions serving as a mimetic of the thiol oxidase enzyme. The nucleophilicity of the bridgehead nitrogen atom in TAAD provides a straightforward way for the conjugation of Fe(IV)-TAAD complexes to various functional molecules. Using this approach, steroidal and peptide molecules having an iron(IV) label have been prepared for the first time. In addition, the Fe(IV)-TAAD complex was covalently bound to a polystyrene matrix and the resulting material was shown to serve as a heterogeneous catalyst for aerobic oxidation of thiols to disulfides.

Golovanov I.S. , Leonov A.V. , Lesnikov V.K. , Pospelov E.V. , Frolov K.V. , Korlyukov A.A. , Nelyubina Y.V. , Novikov V.V. , Sukhorukov A.Y.
Iron(iv) complexes with tetraazaadamantane-based ligands: synthesis, structure, applications in dioxygen activation and labeling of biomolecules
Dalton Transactions. 2022. V.51. N11. P.4284-4296. DOI: 10.1039/d1dt04104e WOS Scopus OpenAlex

Web of science:	WOS:000759009500001
Scopus:	2-s2.0-85126830186
OpenAlex:	W4212922984

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