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.
Mechanistic Aspects of Gas-Phase Hydrogen-Atom Transfer from Methane to [CO].+ and [SiO].+: Why Do They Differ? / Nicolas, Dietl; Troiani, Anna; Maria, Schlangen; Ornella, Ursini; Giancarlo, Angelini; Yitzhak, Apeloig; DE PETRIS, Giulia; Helmut, Schwarz. - In: CHEMISTRY-A EUROPEAN JOURNAL. - ISSN 0947-6539. - STAMPA. - 19:21(2013), pp. 6662-6669. [10.1002/chem.201204157]
Mechanistic Aspects of Gas-Phase Hydrogen-Atom Transfer from Methane to [CO].+ and [SiO].+: Why Do They Differ?
TROIANI, Anna;DE PETRIS, GIULIA;
2013
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.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
