On the role of the electronic structure of the heteronuclear oxide cluster [Ga2Mg2O5 ](.+) in the thermal activation of methane and ethane: an unusual doping effect.
The reactivity of the heteronuclear oxide cluster [Ga2 Mg2 O5 ](.+) , bearing an unpaired electron at a bridging oxygen atom (Ob (.-) ), 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.
Institut für Chemie, Technische Universität Berlin, Strasse des 17. Juni 135, 10623 Berlin (Germany); State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023 (P.R. China).
Jilai
J
Li
Xiao-Nan
XN
Wu
Maria
M
Schlangen
Shaodong
S
Zhou
Patricio
P
González-Navarrete
Shiya
S
Tang
Helmut
H
Schwarz
CH activation; computational chemistry; gas-phase reactions; mass spectrometry; radicals