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Mechanistic aspects of gas-phase hydrogen-atom transfer from methane to [CO](·+) and [SiO](·+) : why do they differ?
Nicolas Dietl1, Anna Troiani, Maria Schlangen
1Institut für Chemie, Technische Universität Berlin, Strasse des 17. Juni 135, 10623 Berlin (Germany).
Abstract:
The reactivity of the two diatomic congeneric systems [CO](·+) and [SiO](·+) towards methane has been investigated by means of mass spectrometry and quantum-chemical calculations. While [CO](·+) gives rise to three different reaction channels, [SiO](·+) reacts only by hydrogen-atom transfer (HAT) from methane under thermal conditions. A theoretical analysis of the respective HAT processes reveals two distinctly different mechanistic pathways for [CO](·+) and [SiO](·+), and a comparison to the higher metal oxides of Group 14 emphasizes the particular role of carbon as a second-row p element.
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