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- W2082332742 endingPage "12321" @default.
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- W2082332742 abstract "Two possible mechanisms for dioxygen cleavage on non-heme diiron enzyme models are studied with an approximate molecular orbital method, the extended Hückel method. Diiron peroxo model complexes with different μ-η1:η1-O2 and μ-η2:η2-O2 binding modes are distorted to corresponding dioxo complexes along an assumed O−O bond cleavage reaction coordinate. Fragment molecular orbital (FMO) and Walsh diagram analyses clarify the bonding and orbital interactions. While the πg* orbitals of O2 are initially occupied by two electrons, in the first dioxygen binding step two other electrons are effectively transferred from the “t2g” block to O2 to form O22-. To cleave the dioxygen O−O bond, it is necessary further to fill the σu* orbital (high lying and unoccupied in the peroxide). The computations suggest that the μ-η1:η1-O2 mode is more effective for electron transfer from the d-block orbitals to the σu*. Our calculations indicate that a C3v- or D2d-distorted methane can be activated if a coordinatively unsaturated iron, which has been proposed to exist in the diamond Fe2(μ-O)2 core of intermediate Q of methane monooxygenase, is generated. The complex is suggested to include a five-coordinate carbon species with an Fe−CH4 bond. We propose possible concerted reaction pathways for the conversion of methane to methanol on the supposed diiron active site of methane monooxygenase. Inversion at a five-coordinate carbon species is suggested to reasonably occur in an initially formed complex of methane and a model of intermediate Q, leading to inversion of stereochemistry at a labeled carbon center." @default.
- W2082332742 created "2016-06-24" @default.
- W2082332742 creator A5001331359 @default.
- W2082332742 creator A5008539128 @default.
- W2082332742 creator A5020839989 @default.
- W2082332742 creator A5059147537 @default.
- W2082332742 date "1997-12-17" @default.
- W2082332742 modified "2023-10-10" @default.
- W2082332742 title "Dioxygen Cleavage and Methane Activation on Diiron Enzyme Models: A Theoretical Study" @default.
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- W2082332742 doi "https://doi.org/10.1021/ja9726419" @default.
- W2082332742 hasPublicationYear "1997" @default.