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Treatment of Mn(N(SiMe 3 ) 2 ) 2 (THF) 2 with bulky chelating bis(alkoxide) ligand [1,1':4',1''-terphenyl]-2,2''-diylbis(diphenylmethanol) (H 2 [O-terphenyl-O] Ph ) formed a seesaw manganese(II) complex Mn[O-terphenyl-O] Ph (THF) 2 , characterized by structural, spectroscopic, magnetic, and analytical methods. The reactivity of Mn[O-terphenyl-O] Ph (THF) 2 with various nitrene precursors was investigated. No reaction was observed between Mn[O-terphenyl-O] Ph (THF) 2 and aryl azides. In contrast, the treatment of Mn[O-terphenyl-O] Ph (THF) 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] Ph (THF) 2 at room temperature produced 2-phenylaziridine in up to a 79% yield. Exploration of the reactivity of Mn[O-terphenyl-O] Ph (THF) 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.

Aziridination Reactivity of a Manganese(II) Complex with a Bulky Chelating Bis(Alkoxide) Ligand