{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T01:17:17Z","timestamp":1760145437096,"version":"build-2065373602"},"reference-count":46,"publisher":"MDPI AG","issue":"15","license":[{"start":{"date-parts":[[2024,7,24]],"date-time":"2024-07-24T00:00:00Z","timestamp":1721779200000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>Transition-metal-catalyzed nitrene transfer reactions are typically performed in organic solvents under inert and anhydrous conditions due to the involved air and water-sensitive nature of reactive intermediates. Overall, this study provides insights into the iron-based ([FeII(PBI)3](CF3SO3)2 (1), where PBI = 2-(2-pyridyl)benzimidazole), catalytic and stoichiometric aziridination of styrenes using PhINTs ([(N-tosylimino)iodo]benzene), highlighting the importance of reaction conditions including the effects of the solvent, co-ligands (para-substituted pyridines), and substrate substituents on the product yields, selectivity, and reaction kinetics. The aziridination reactions with 1\/PhINTs showed higher conversion than epoxidation with 1\/PhIO (iodosobenzene). However, the reaction with PhINTs was less selective and yielded more products, including styrene oxide, benzaldehyde, and 2-phenyl-1-tosylaziridine. Therefore, the main aim of this study was to investigate the potential role of water in the formation of oxygen-containing by-products during radical-type nitrene transfer catalysis. During the catalytic tests, a lower yield was obtained in a protic solvent (trifluoroethanol) than in acetonitrile. In the case of the catalytic oxidation of para-substituted styrenes containing electron-donating groups, higher yield, TON, and TOF were achieved than those with electron-withdrawing groups. Pseudo-first-order kinetics were observed for the stoichiometric oxidation, and the second-order rate constants (k2 = 7.16 \u00d7 10\u22123 M\u22121 s\u22121 in MeCN, 2.58 \u00d7 10\u22123 M\u22121 s\u22121 in CF3CH2OH) of the reaction were determined. The linear free energy relationships between the relative reaction rates (logkrel) and the total substituent effect (TE, 4R-PhCHCH2) parameters with slopes of 1.48 (MeCN) and 1.89 (CF3CH2OH) suggest that the stoichiometric aziridination of styrenes can be described through the formation of a radical intermediate in the rate-determining step. Styrene oxide formation during aqueous styrene aziridination most likely results from oxygen atom transfer via in situ iron oxo\/oxyl radical complexes, which are formed through the hydrolysis of [FeIII(N\u2022Ts)] under experimental conditions.<\/jats:p>","DOI":"10.3390\/molecules29153470","type":"journal-article","created":{"date-parts":[[2024,7,24]],"date-time":"2024-07-24T15:47:32Z","timestamp":1721836052000},"page":"3470","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["A Mechanistic Study on Iron-Based Styrene Aziridination: Understanding Epoxidation via Nitrene Hydrolysis"],"prefix":"10.3390","volume":"29","author":[{"given":"D\u00f3ra","family":"Lakk-Bog\u00e1th","sequence":"first","affiliation":[{"name":"Research Group of Bioorganic and Bio-Coordination Chemistry, University of Pannonia, H-8201 Veszpr\u00e9m, Hungary"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Patrik","family":"T\u00f6r\u00f6k","sequence":"additional","affiliation":[{"name":"Research Group of Bioorganic and Bio-Coordination Chemistry, University of Pannonia, H-8201 Veszpr\u00e9m, Hungary"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"D\u00e9nes","family":"Pintarics","sequence":"additional","affiliation":[{"name":"Research Group of Bioorganic and Bio-Coordination Chemistry, University of Pannonia, H-8201 Veszpr\u00e9m, Hungary"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1427-8105","authenticated-orcid":false,"given":"J\u00f3zsef","family":"Kaizer","sequence":"additional","affiliation":[{"name":"Research Group of Bioorganic and Bio-Coordination Chemistry, University of Pannonia, H-8201 Veszpr\u00e9m, Hungary"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2024,7,24]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"1693","DOI":"10.1016\/S0957-4166(97)00177-8","article-title":"The asymmetric synthesis of aziridines","volume":"8","author":"Osborn","year":"1997","journal-title":"Tetrahedron Asymmetry"},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"7881","DOI":"10.1021\/cr400553c","article-title":"Recent Advances in the Stereoselective Synthesis of Aziridines","volume":"114","author":"Degennaro","year":"2014","journal-title":"Chem. 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