Mechanistic Insight into the Nitric Oxide Dioxygenation Reaction of Nonheme Iron(III)–Superoxo and Manganese(IV)–Peroxo Complexes

Seungwoo Hong, Pankaj Kumar, Kyung Bin Cho, Yong Min Lee, Kenneth D. Karlin, Wonwoo Nam

Research output: Contribution to journalArticlepeer-review

10 Scopus citations

Abstract

Reactions of nonheme FeIII–superoxo and MnIV–peroxo complexes bearing a common tetraamido macrocyclic ligand (TAML), namely [(TAML)FeIII(O2)]2−and [(TAML)MnIV(O2)]2−, with nitric oxide (NO) afford the FeIII–NO3complex [(TAML)FeIII(NO3)]2−and the MnV–oxo complex [(TAML)MnV(O)]plus NO2, respectively. Mechanistic studies, including density functional theory (DFT) calculations, reveal that MIII–peroxynitrite (M=Fe and Mn) species, generated in the reactions of [(TAML)FeIII(O2)]2−and [(TAML)MnIV(O2)]2−with NO, are converted into MIV(O) and.NO2species through O−O bond homolysis of the peroxynitrite ligand. Then, a rebound of FeIV(O) with.NO2affords [(TAML)FeIII(NO3)]2−, whereas electron transfer from MnIV(O) to.NO2yields [(TAML)MnV(O)]plus NO2.

Original languageEnglish
Pages (from-to)12403-12407
Number of pages5
JournalAngewandte Chemie - International Edition
Volume55
Issue number40
DOIs
StatePublished - 26 Sep 2016

Keywords

  • biomimetic chemistry
  • iron
  • manganese
  • nonheme metal–oxo complexes
  • reactive nitrogen species

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