title: Mechanistic aspects of gas-phase hydrogen-atom transfer from methane to [CO](·+) and [SiO](·+) : why do they differ?
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.
authors.affiliation: Institut für Chemie, Technische Universität Berlin, Strasse des 17. Juni 135, 10623 Berlin (Germany).
authors.forename: Nicolas
authors.initials: N
authors.lastname: Dietl
authors.forename: Anna
authors.initials: A
authors.lastname: Troiani
authors.forename: Maria
authors.initials: M
authors.lastname: Schlangen
authors.forename: Ornella
authors.initials: O
authors.lastname: Ursini
authors.forename: Giancarlo
authors.initials: G
authors.lastname: Angelini
authors.forename: Yitzhak
authors.initials: Y
authors.lastname: Apeloig
authors.forename: Giulia
authors.initials: G
authors.lastname: de Petris
authors.forename: Helmut
authors.initials: H
authors.lastname: Schwarz
mesh_terms: D002248:Carbon Monoxide / Q000737:chemistry*; D005740:Gases / Q000737:chemistry; D006859:Hydrogen / Q000737:chemistry; D008697:Methane / Q000737:chemistry*; D008956:Models, Chemical; D010087:Oxides / Q000737:chemistry*; D017655:Silicon Compounds / Q000737:chemistry*; D013816:Thermodynamics
chemical_list: D005740:Gases; D010087:Oxides; D017655:Silicon Compounds; C116473:silicon monoxide; D002248:Carbon Monoxide; D006859:Hydrogen; D008697:Methane