Details

Autor(en) / Beteiligte

• Golovanov, Ivan S
• Leonov, Anton V
• Lesnikov, Vladislav K
• Pospelov, Evgeny V
• Frolov, Kirill V
• Korlyukov, Alexander A
• Nelyubina, Yulia V
• Novikov, Valentin V
• Sukhorukov, Alexey Yu

Titel

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

Ist Teil von

• Dalton transactions : an international journal of inorganic chemistry, 2022-03, Vol.51 (11), p.4284-4296

Ort / Verlag

England: Royal Society of Chemistry

Erscheinungsjahr

2022

Quelle

MEDLINE

Beschreibungen/Notizen

• 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 d 4 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. This paper describes a unique example of a stable non-heme iron( iv ) complex formed by oxidation with air. The complex enables dioxygen activation by serving as a mimetic of thiol oxidase.