TY - JOUR
T1 - Oxygen activation at mononuclear nonheme iron centers
T2 - A superoxo perspective
AU - Mukherjee, Anusree
AU - Cranswick, Matthew A.
AU - Chakrabarti, Mrinmoy
AU - Paine, Tapan K.
AU - Fujisawa, Kiyoshi
AU - Münck, Eckard
AU - Que, Lawrence
PY - 2010/4/19
Y1 - 2010/4/19
N2 - Dioxygen (O2) activation by iron enzymes is responsible for many metabolically important transformations in biology. Often a high-valent iron oxo oxidant is proposed to form upon O2 activation at a mononuclear nonheme iron center, presumably via intervening iron superoxo and iron peroxo species. While iron(IV) oxo intermediates have been trapped and characterized in enzymes and models, less is known of the putative iron(III) superoxo species. Utilizing a synthetic model for the 2-oxoglutarate-dependent monoiron enzymes, [(TpiPr2)FeII(O2CC(O)CH3)], we have obtained indirect evidence for the formation of the putative iron(III) superoxo species, which can undergo one-electron reduction, hydrogen-atom transfer, or conversion to an iron(IV) oxo species, depending on the reaction conditions. These results demonstrate the various roles that the iron(III) superoxo species can play in the course of O2 activation at a nonheme iron center.
AB - Dioxygen (O2) activation by iron enzymes is responsible for many metabolically important transformations in biology. Often a high-valent iron oxo oxidant is proposed to form upon O2 activation at a mononuclear nonheme iron center, presumably via intervening iron superoxo and iron peroxo species. While iron(IV) oxo intermediates have been trapped and characterized in enzymes and models, less is known of the putative iron(III) superoxo species. Utilizing a synthetic model for the 2-oxoglutarate-dependent monoiron enzymes, [(TpiPr2)FeII(O2CC(O)CH3)], we have obtained indirect evidence for the formation of the putative iron(III) superoxo species, which can undergo one-electron reduction, hydrogen-atom transfer, or conversion to an iron(IV) oxo species, depending on the reaction conditions. These results demonstrate the various roles that the iron(III) superoxo species can play in the course of O2 activation at a nonheme iron center.
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U2 - 10.1021/ic901891n
DO - 10.1021/ic901891n
M3 - Article
C2 - 20380464
AN - SCOPUS:77950977884
SN - 0020-1669
VL - 49
SP - 3618
EP - 3628
JO - Inorganic chemistry
JF - Inorganic chemistry
IS - 8
ER -