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- Title
Modelling on a Biomimetic [Cu−O−Cu]<sup>2+</sup>–mediated Methane–to–Methanol Conversion Unveils the Site for Methane Activation.
- Authors
Arora, Sumangla; Gupta, Puneet
- Abstract
The Cu−O−Cu core exhibits methane‐to‐methanol conversion, mirroring the reactivity of the copper–containing enzyme pMMO. Herein, we computationally examined the reactivity of a biomimetic Cu−O−Cu core towards methane–to–methanol conversion. The oxygen atom of the Cu−O−Cu core abstracts hydrogen present in the C−H bond of methane. The spin density at the bridging oxygen helps to abstract hydrogen from the C−H bond. We modulated the spin density of the bridging oxygen by substituting only a single copper atom of the Cu−O−Cu core by metals (M) such as Fe, Co, and Ag. These substitutions result in bimetallic [Cu−O−M]2+ models. We observed that the energy barriers for the C−H activation step and the subsequent rebound step vary with the metal M. [Cu−O−Ag]2+ exhibits the highest reactivity for M2M conversion, while [Cu−O−Fe]2+ displays the lowest reactivity. To understand the different reactivity of these models towards M2M conversion, we employed distortion‐interaction analysis, orbital analysis, spin density analysis, and quantum theory of atoms in molecules analysis. Orbital analysis reveals that all four adducts follow a hydrogen atom transfer mechanism for C−H activation. Further, spin density analysis reveals that a higher spin density on the bridging oxygen leads to a lower C−H activation barrier.
- Subjects
ATOMS in molecules theory; ABSTRACTION reactions; COPPER; OXYGEN; ACTIVATION energy; METHANE
- Publication
Chemistry - An Asian Journal, 2024, Vol 19, Issue 14, p1
- ISSN
1861-4728
- Publication type
Article
- DOI
10.1002/asia.202400282