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- Title
Mechanistic Insight into the Nitric Oxide Dioxygenation Reaction of Nonheme Iron(III)-Superoxo and Manganese(IV)-Peroxo Complexes.
- Authors
Hong, Seungwoo; Kumar, Pankaj; Cho, Kyung ‐ Bin; Lee, Yong ‐ Min; Karlin, Kenneth D.; Nam, Wonwoo
- 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-NO3 complex [(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 .NO2 species through O−O bond homolysis of the peroxynitrite ligand. Then, a rebound of FeIV(O) with .NO2 affords [(TAML)FeIII(NO3)]2−, whereas electron transfer from MnIV(O) to .NO2 yields [(TAML)MnV(O)]− plus NO2−.
- Subjects
NITRIC oxide; OXYGENATION (Chemistry); IRON compounds; LIGANDS (Chemistry); DENSITY functional theory; CHARGE exchange
- Publication
Angewandte Chemie, 2016, Vol 128, Issue 40, p12591
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.201605705