Mononuclear Manganese(III) Superoxo Complexes: Synthesis, Characterization, and Reactivity

Metal-superoxo species are typically proposed as key intermediates in the catalytic cycle of dioxygen activation by metalloenzymes involving different transition metal cofactors. In this regard, while a series of Fe-, Co-, and Ni-superoxo complexes have been reported to date, well-defined Mn-superoxo complexes remain rather rare. Herein, we report two mononuclear Mn^III-superoxo species, Mn(BDPP)(O₂^•-) (2, H₂BDPP = 2,6-bis((2-(S)-diphenylhydroxylmethyl-1-pyrrolidinyl)methyl)pyridine) and Mn(BDP^BrP)(O₂^•-) (2', H₂BDP^BrP = 2,6-bis((2-(S)-di(4-bromo)phenylhydroxyl-methyl-1-pyrrolidinyl)methyl)pyridine), synthesized by bubbling O₂ into solutions of their Mn^II precursors, Mn(BDPP) (1) and Mn(BDP^BrP) (1'), at -80 °C. A combined spectroscopic (resonance Raman and electron paramagnetic resonance (EPR) spectroscopy) and computational study evidence that both complexes contain a high-spin Mn^III center (S_Mn = 2) antiferromagnetically coupled to a superoxo radical ligand (S_OO• = 1/2), yielding an overall S = 3/2 ground state. Complexes 2 and 2' were shown to be capable of abstracting a H atom from 2,2,6,6-tetramethyl-1-hydroxypiperidine (TEMPO-H) to form Mn^III-hydroperoxo species, Mn(BDPP)(OOH) (5) and Mn(BDP^BrP)(OOH) (5'). Complexes 5 and 5' can be independently prepared by the reactions of the isolated Mn^III-aqua complexes, [Mn(BDPP)(H₂O)]OTf (6) and [Mn(BDP^BrP)(H₂O)]OTf (6'), with H₂O₂ in the presence of NEt₃. The parallel-mode EPR measurements established a high-spin S = 2 ground state for 5 and 5'.