Exploring the nitric oxide dioxygenation (NOD) reactions of manganese-peroxo complexes.

Here, we report the nitric oxide dioxygenation (NOD) reactions of two Mn-peroxo (M-O) complexes, [(3PYENMe)Mn(O)] (1) and [(N3PY)Mn(O)] (2), bearing pentadentate ligands. Complexes 1 and 2 give Mn-nitrate (Mn-NO) complexes (3 and 4) when reacted with nitric oxide (NO), respectively. The mechanistic study explored by using 2,4-di--butylphenol (2,4-DTBP) suggested that the NOD reaction of 1 and 2 occurs a presumed Mn-peroxynitrite ([Mn-PN], [Mn-ONOO]) intermediate. Tracking the source of N atoms using NO revealed that the N-atoms in Mn-NO (3 and 4) are derived from the NO moiety. Furthermore, we have explored the M-O regeneration from NOD products (3 and 4), and we have observed the formation of M-O complexes (1 and 2) upon treatment with KO or HO/triethylamine (TEA), respectively.