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Министерство науки и высшего образования Российской Федерации
Российская Академия Наук

New stable iron (IV) complex was synthesized in ZIOC

21 march 2022 г.

High-valent iron compounds play an important role in biological processes associated with catalytic activation cycles of molecular oxygen. Currently, scientists around the world are actively developing artificial catalysts with similar properties for use in aerobic oxidation reactions of various organic compounds. However, Fe(IV) complexes synthesized under laboratory conditions are, as a rule, unstable in air and water, which significantly complicates their use.

Scientists from the Laboratory of Organic and Metal-Organic Nitrogen-Oxygen Systems of the ZIOC in collaboration with colleagues from the Nesmeyanov Institute of Organoelement Compounds and the Shubnikov Institute of Crystallography have obtained a new stable Fe(IV) complex with a tris-hydroxylamine ligand. Structural and electronic features of the resulting complex were studied using a wide range of modern physicochemical methods, including paramagnetic NMR spectroscopy, X-ray diffraction analysis, Mössbauer spectroscopy, etc. Due to the presence of a nucleophilic nitrogen atom in the complex, it is possible to carry out its chemical modification, which was demonstrated by the example of the synthesis of steroid and peptide derivatives of iron(IV) complexes, as well as their immobilization on a solid polystyrene substrate. In the course of research, the ability of the obtained compounds to catalyze the process of aerobic oxidation of thiols to disulfides, by analogy with the enzyme thiol oxidase, was also discovered.

 

Source:

Ivan S. Golovanov, Anton V. Leonov, Vladislav K. Lesnikov, Evgeny V. Pospelov, Kirill V. Frolov, Alexander A. Korlyukov, Yulia V. Nelyubina, Valentin V. Novikov, Alexey Yu. Sukhorukov Iron(IV) complexes with tetraazaadamantane-based ligands: synthesis, structure, applications in dioxygen activation and labeling of biomolecules. Dalton Trans., 2022, 51, 4284-4296. DOI: 10.1039/d1dt04104e.