On the Role of the Electronic Structure of the Heteronuclear Oxide Cluster [Ga2Mg2O5].+ in the Thermal Activation of Methane and Ethane: An Unusual Doping Effect1. Issue 17 (27th February 2015)

• Record Type: Journal Article
• Authors: Li, Jilai; Wu, Xiao‐Nan; Schlangen, Maria; Zhou, Shaodong; González‐Navarrete, Patricio; Tang, Shiya; Schwarz, Helmut
• Is Part Of: Angewandte Chemie international edition. Volume 54:Issue 17(2015)
• Page Start: 5074
• Page End: 5078
• Publication Date: 2015-02-27
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201412441
• Languages: English
• ISSNs: 1433-7851

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>The reactivity of the heteronuclear oxide cluster [Ga₂Mg₂O₅]^.+, 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 CH bond activation but also provide important guidance for the rational design of catalysts by pointing to the particular role of doping effects.</p> </abstract>