Aziridination Reactivity of a Manganese Ligand

• Published in: Molecules (Basel, Switzerland) Switzerland), 2022-09, Vol.27 (18)
• Main Authors: Kurup, Sudheer S, Woodland, Natalie M, Lord, Richard L, Groysman, Stanislav
• Format: Article
• Language: English
• Subjects: Aziridines; Chelating agents; Chemical properties; Manganese; Organic compounds; Synthesis
• ISSN: 1420-3049; 1420-3049
• DOI: 10.3390/molecules27185751

Treatment of Mn(N(SiMe[sub.3] )[sub.2] )[sub.2] (THF)[sub.2] with bulky chelating bis(alkoxide) ligand [1,1′:4′,1′′-terphenyl]-2,2′′-diylbis(diphenylmethanol) (H[sub.2] [O-terphenyl-O][sup.Ph] ) formed a seesaw manganese(II) complex Mn[O-terphenyl-O][sup.Ph] (THF)[sub.2] , characterized by structural, spectroscopic, magnetic, and analytical methods. The reactivity of Mn[O-terphenyl-O][sup.Ph] (THF)[sub.2] with various nitrene precursors was investigated. No reaction was observed between Mn[O-terphenyl-O][sup.Ph] (THF)[sub.2] and aryl azides. In contrast, the treatment of Mn[O-terphenyl-O][sup.Ph] (THF)[sub.2] with iminoiodinane PhINTs (Ts = p-toluenesulfonyl) was consistent with the formation of a metal-nitrene complex. In the presence of styrene, the reaction led to the formation of aziridine. Combining varying ratios of styrene and PhINTs in different solvents with 10 mol% of Mn[O-terphenyl-O][sup.Ph] (THF)[sub.2] at room temperature produced 2-phenylaziridine in up to a 79% yield. Exploration of the reactivity of Mn[O-terphenyl-O][sup.Ph] (THF)[sub.2] with various olefins revealed (1) moderate aziridination yields for p-substituted styrenes, irrespective of the electronic nature of the substituent; (2) moderate yield for 1,1′-disubstituted α-methylstyrene; (3) no aziridination for aliphatic α-olefins; (4) complex product mixtures for the β-substituted styrenes. DFT calculations suggest that iminoiodinane is oxidatively added upon binding to Mn, and the resulting formal imido intermediate has a high-spin Mn(III) center antiferromagnetically coupled to an imidyl radical. This imidyl radical reacts with styrene to form a sextet intermediate that readily reductively eliminates the formation of a sextet Mn(II) aziridine complex.