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On the Role of the Electronic Structure of the Heteronuclear Oxide Cluster [Ga 2 Mg 2 O 5 ] .+ in the Thermal Activation of Methane and Ethane: An Unusual Doping Effect
Author(s) -
Li Jilai,
Wu XiaoNan,
Schlangen Maria,
Zhou Shaodong,
GonzálezNavarrete Patricio,
Tang Shiya,
Schwarz Helmut
Publication year - 2015
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201412441
Subject(s) - heteronuclear molecule , chemistry , fourier transform ion cyclotron resonance , reactivity (psychology) , unpaired electron , oxide , density functional theory , hydrogen atom , ion , analytical chemistry (journal) , inorganic chemistry , molecule , computational chemistry , nuclear magnetic resonance spectroscopy , stereochemistry , organic chemistry , alternative medicine , pathology , medicine , alkyl
The reactivity of the heteronuclear oxide cluster [Ga 2 Mg 2 O 5 ] .+ , bearing an unpaired electron at a bridging oxygen atom (O b .− ), towards methane and ethane has been studied using Fourier transform ion cyclotron resonance mass spectrometry (FT‐ICR‐MS). Hydrogen‐atom transfer (HAT) from both methane and ethane to the cluster ion is identified experimentally. The reaction mechanisms of these reactions are elucidated by state‐of‐the‐art quantum chemical calculations. The roles of spin density and charge distributions in HAT processes, as revealed by theory, not only deepen our mechanistic understanding of CH bond activation but also provide important guidance for the rational design of catalysts by pointing to the particular role of doping effects.