Mechanistic Insight into the Nitric Oxide Dioxygenation Reaction of Nonheme Iron(III)–Superoxo and Manganese(IV)–Peroxo Complexes |
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| Authors: | Dr Seungwoo Hong Dr Pankaj Kumar Dr Kyung‐Bin Cho Dr Yong‐Min Lee Prof?Dr Kenneth D Karlin Prof?Dr Wonwoo Nam |
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| Affiliation: | 1. Department of Chemistry and Nano Science, Ewha Womans University, Seoul, Korea;2. The Johns Hopkins University, Baltimore, MD, USA |
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| 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?. |
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| Keywords: | biomimetic chemistry iron manganese nonheme metal– oxo complexes reactive nitrogen species |
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