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Thermal Methane Activation by [Si 2 O 5 ] .+ and [Si 2 O 5 H 2 ] .+ : Reactivity Enhancement by Hydrogenation
Author(s) -
Sun Xiaoyan,
Zhou Shaodong,
Schlangen Maria,
Schwarz Helmut
Publication year - 2016
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.201607864
Subject(s) - reactivity (psychology) , methane , chemistry , ion , analytical chemistry (journal) , hydrogen , cluster (spacecraft) , fourier transform ion cyclotron resonance , mass spectrometry , inorganic chemistry , medicine , alternative medicine , organic chemistry , pathology , chromatography , computer science , programming language
Abstract The thermal reactions of methane with the oxygen‐rich cluster cations [Si 2 O 5 ] ⋅+ and [Si 2 O 5 H 2 ] ⋅+ have been examined using Fourier transform–ion cyclotron resonance (FT‐ICR) mass spectrometry in conjunction with state‐of‐the‐art quantum chemical calculations. In contrast to the inertness of [Si 2 O 5 ] .+ towards methane, the hydrogenated cluster [Si 2 O 5 H 2 ] .+ brings about hydrogen‐atom transfer (HAT) from methane with an efficiency of 28 % relative to the collision rate. The mechanisms of this process have been investigated in detail and the reasons for the striking reactivity difference of the two cluster ions have been revealed.