Mechanistic Aspects of Gas‐Phase Hydrogen‐Atom Transfer from Methane to [CO].+ and [SiO].+: Why Do They Differ?. Issue 21 (27th March 2013)

• Record Type: Journal Article
• Authors: Dietl, Nicolas; Troiani, Anna; Schlangen, Maria; Ursini, Ornella; Angelini, Giancarlo; Apeloig, Yitzhak; de Petris, Giulia; Schwarz, Helmut
• Is Part Of: Chemistry. Volume 19:Issue 21(2013)
• Page Start: 6662
• Page End: 6669
• Publication Date: 2013-03-27
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201204157
• Languages: English
• ISSNs: 0947-6539

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>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.</p> </abstract>