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• W2148900521 endingPage "6567" @default.
• W2148900521 startingPage "6555" @default.
• W2148900521 abstract "Abstract α‐Ketoglutarate (αKG)‐dependent nonheme iron enzymes utilize a high‐spin (HS) ferrous center to couple the activation of oxygen to the decarboxylation of the cosubstrate αKG to yield succinate and CO 2 , and to generate a high‐valent ferryl species that then acts as an oxidant to functionalize the target CH bond. Herein a detailed analysis of the electronic‐structure changes that occur in the oxygen activation by this enzyme was performed. The rate‐limiting step, which is identical on the septet and quintet surfaces, is the nucleophilic attack of the distal O atom of the O 2 adduct on the carbonyl group in αKG through a bicyclic transition state ( 5, 7 TS1). Due to the different electronic structures in 5, 7 TS1, the decay of 7 TS1 leads to a ferric oxyl species, which undergoes a rapid intersystem crossing to form the ferryl intermediate. By contrast, a HS ferrous center ligated by a peroxosuccinate is obtained on the quintet surface following 5 TS1. Thus, additional two single‐electron transfer steps are required to afford the same Fe IV –oxo species. However, the triplet reaction channel is catalytically irrelevant. The biological role of αKG played in the oxygen‐activation reaction is dual. The αKG LUMO (CO π*) serves as an electron acceptor for the nucleophilic attack of the superoxide monoanion. On the other hand, the αKG HOMO (C1C2 σ) provides the second and third electrons for the further reduction of the superoxide. In addition to density functional theory, high‐level ab initio calculations have been used to calculate the accurate energies of the critical points on the alternative potential‐energy surfaces. Overall, the results delivered by the ab initio calculations are largely parallel to those obtained with the B3LYP density functional, thus lending credence to our conclusions." @default.
• W2148900521 created "2016-06-24" @default.
• W2148900521 creator A5001152854 @default.
• W2148900521 creator A5046820685 @default.
• W2148900521 creator A5048115968 @default.
• W2148900521 creator A5050467129 @default.
• W2148900521 creator A5064712476 @default.
• W2148900521 creator A5076704150 @default.
• W2148900521 date "2012-04-18" @default.
• W2148900521 modified "2023-10-18" @default.
• W2148900521 title "Electronic Structure Analysis of the Oxygen-Activation Mechanism by Fe^II- and α-Ketoglutarate (αKG)-Dependent Dioxygenases" @default.
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