3 years ago

Electronic Origin of the Competitive Mechanisms in the Thermal Activation of Methane by the Heteronuclear Cluster Oxide [Al2ZnO4].+

Electronic Origin of the Competitive Mechanisms in the Thermal Activation of Methane by the Heteronuclear Cluster Oxide [Al2ZnO4].+
Lei Yue, Shaodong Zhou, Helmut Schwarz, Maria Schlangen
The thermal gas-phase reactions of [Al2ZnO4].+ with methane have been explored by using FT-ICR mass spectrometry complemented by high-level quantum chemical calculations. Two competitive mechanisms, that is, hydrogen-atom transfer (HAT) and proton-coupled electron transfer (PCET) are operative. Interestingly, while the HAT process is influenced by the polarity of the transition structure, both the ionic nature of the metal–oxygen bond and the structural rigidity of the cluster oxide affect the PCET pathway. As compared to the previously reported homonuclear [Al2O3].+ and [ZnO].+, the heteronuclear oxide [Al2ZnO4].+ exhibits a much higher chemoselectivity towards methane. The electronic origins of the doping effect have been explored. Choose your path: The two mechanistic variants in the thermal reaction of [Al2ZnO4].+ with methane are identified: a hydrogen atom transfer (HAT) and a proton-coupled electron transfer (PCET). While the PCET reaction is influenced by the ionic character of the metal–oxygen bond, the HAT process depends on the polarity of the transition structure.

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

DOI: 10.1002/anie.201704979

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