Trapping and spectroscopic characterization of an FeIII-superoxo intermediate from a nonheme mononuclear iron-containing enzyme
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چکیده
منابع مشابه
Characterization of a Paramagnetic Mononuclear Nonheme Iron-Superoxo Complex
O2 bubbling into a THF solution of Fe(II)(BDPP) (1) at -80 °C generates a reversible bright yellow adduct 2. Characterization by resonance Raman and Mössbauer spectroscopy provides complementary insights into the nature of 2. The former shows a resonance-enhanced vibration at 1125 cm(-1), which can be assigned to the ν(O-O) of a bound superoxide, while the latter reveals the presence of a high-...
متن کاملIdentification and Spectroscopic Characterization of Nonheme Iron(III) Hypochlorite Intermediates†
Fe(III)-hypohalite complexes have been implicated in a wide range of important enzyme-catalyzed halogenation reactions including the biosynthesis of natural products and antibiotics and post-translational modification of proteins. The absence of spectroscopic data on such species precludes their identification. Herein, we report the generation and spectroscopic characterization of nonheme Fe(II...
متن کاملSpectroscopic Characterization and Reactivity Studies of a Mononuclear Nonheme Mn(III)–Hydroperoxo Complex
We report the first example of a mononuclear nonheme manganese(III)-hydroperoxo complex derived from protonation of an isolated manganese(III)-peroxo complex bearing an N-tetramethylated cyclam (TMC) ligand, [Mn(III)(TMC)(OOH)](2+). The Mn(III)-hydroperoxo intermediate is characterized with various spectroscopic methods as well as with density functional theory (DFT) calculations, showing the b...
متن کاملRegioselectivity of aliphatic versus aromatic hydroxylation by a nonheme iron(II)-superoxo complex.
Many enzymes in nature utilize molecular oxygen on an iron center for the catalysis of substrate hydroxylation. In recent years, great progress has been made in understanding the function and properties of iron(IV)-oxo complexes; however, little is known about the reactivity of iron(II)-superoxo intermediates in substrate activation. It has been proposed recently that iron(II)-superoxo intermed...
متن کاملNonheme iron-oxo and -superoxo reactivities: O2 binding and spin inversion probability matter.
DFT calculated barriers for C-H activation of 1,4-cyclohexadiene by nonheme iron(IV)-oxo and iron(III)-superoxo species show that the experimental trends can be explained if the spin inversion probability of the TMC iron(IV)-oxo is assumed to be poor. Also, the TMC iron(III)-superoxo reaction proceeds with an endothermic O(2)-binding energy followed by an intrinsically reactive quintet state.
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ژورنال
عنوان ژورنال: Proceedings of the National Academy of Sciences
سال: 2010
ISSN: 0027-8424,1091-6490
DOI: 10.1073/pnas.1010015107