Mechanistic Insight into the Nitric Oxide Dioxygenation Reaction of Nonheme Iron(III)-Superoxo and Manganese(IV)-Peroxo Complexes.
Reactions of nonheme Fe(III) -superoxo and Mn(IV) -peroxo complexes bearing a common tetraamido macrocyclic ligand (TAML), namely [(TAML)Fe(III) (O2 )](2-) and [(TAML)Mn(IV) (O2 )](2-) , with nitric oxide (NO) afford the Fe(III) -NO3 complex [(TAML)Fe(III) (NO3 )](2-) and the Mn(V) -oxo complex [(TAML)Mn(V) (O)](-) plus NO2 (-) , respectively. Mechanistic studies, including density functional theory (DFT) calculations, reveal that M(III) -peroxynitrite (M=Fe and Mn) species, generated in the reactions of [(TAML)Fe(III) (O2 )](2-) and [(TAML)Mn(IV) (O2 )](2-) with NO, are converted into M(IV) (O) and (.) NO2 species through O-O bond homolysis of the peroxynitrite ligand. Then, a rebound of Fe(IV) (O) with (.) NO2 affords [(TAML)Fe(III) (NO3 )](2-) , whereas electron transfer from Mn(IV) (O) to (.) NO2 yields [(TAML)Mn(V) (O)](-) plus NO2 (-) .
Department of Chemistry and Nano Science, Ewha Womans University, Seoul, 03760, Korea.
Seungwoo
S
Hong
Department of Chemistry and Nano Science, Ewha Womans University, Seoul, 03760, Korea.
Pankaj
P
Kumar
Department of Chemistry and Nano Science, Ewha Womans University, Seoul, 03760, Korea.
Kyung-Bin
KB
Cho
Department of Chemistry and Nano Science, Ewha Womans University, Seoul, 03760, Korea.
Yong-Min
YM
Lee
The Johns Hopkins University, Baltimore, MD, 21218, USA. karlin@jhu.edu.
Kenneth D
KD
Karlin
Department of Chemistry and Nano Science, Ewha Womans University, Seoul, 03760, Korea. wwnam@ewha.ac.kr.
Wonwoo
W
Nam
D040761:Biomimetic Materials / Q000737:chemistry / Q000378:metabolism; D056831:Coordination Complexes / Q000737:chemistry* / Q000378:metabolism; D004579:Electron Transport; D007477:Ions / Q000737:chemistry; D007501:Iron / Q000737:chemistry*; D008024:Ligands; D008345:Manganese / Q000737:chemistry*; D008958:Models, Molecular; D009569:Nitric Oxide / Q000737:chemistry* / Q000378:metabolism; D010100:Oxygen / Q000737:chemistry; D013056:Spectrophotometry, Ultraviolet
D056831:Coordination Complexes; D007477:Ions; D008024:Ligands; D009569:Nitric Oxide; D008345:Manganese; D007501:Iron; D010100:Oxygen
biomimetic chemistry; iron; manganese; nonheme metal-oxo complexes; reactive nitrogen species