5 years ago

Control of Product Distribution and Mechanism by Ligation and Electric Field in the Thermal Activation of Methane

Control of Product Distribution and Mechanism by Ligation and Electric Field in the Thermal Activation of Methane
Lei Yue, Jilai Li, Sason Shaik, Shaodong Zhou, Helmut Schwarz, Xiaoyan Sun, Maria Schlangen
Selective oxidative coupling of methane using metal–oxide-based catalysts constitutes one of the central challenges in the valorization of this inert hydrocarbon. Ligands have been known for decades to profoundly affect the electronic character of metal centers with the benefit to fine-tune the chemical features of, for example, cationic metal oxides. A well-studied case concerns the axial-ligand effect exerted in iron–oxo complexes, wherein by changing the electronic structure, the axial ligand fine-tunes the reactivity. However, the electronic origin of ligand effects in the gas-phase C−H bond activation, mediated by metal–oxide catalysts, is not understood very well yet. A simple ligand turns off two of the three channels operative in the [ZnO].+/CH4 couple. As a result, only hydrogen-atom abstraction occurs for the [(CH3CN)ZnO].+/CH4 system. This remarkable ligand effect can be modeled well by an oriented external electric field. PCSET: proton-coupled single-electron transfer; OEEF: oriented external electric field; HAT: hydrogen-atom transfer.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/anie.201703485

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