Methane activation by metal-free radical cations: experimental insight into the reaction intermediate.
A precise jab to methane: The SO(2)(*+) radical cation (see figure) effectively activates CH(4) at room temperature through a [H(3)C(*)...HOSO(+)] methyl intermediate isolated in the gas phase by mass spectrometry. Methanol and ionized methyl hydrogen sulfoxylate, CH(3)OSOH(*+), are formed by selective, direct attack of the incipient methyl radical at the O atom of the intermediate. The reaction shows radical and charge effects in the activation of methane by metal-free radical cations.
de Petris
Giulia
G
Dipartimento di Chimica e Tecnologie del Farmaco, Università La Sapienza, P.le Aldo Moro 5, 00185 Roma, Italy. giulia.depetris@uniroma1.it
Troiani
Anna
A
Rosi
Marzio
M
Angelini
Giancarlo
G
Ursini
Ornella
O
D002412:Cations; D008697:Methane / Q000737:chemistry*; D008956:Models, Chemical; D013463:Sulfuric Acid Esters / Q000737:chemistry*; D053719:Tandem Mass Spectrometry / Q000379:methods*; D013816:Thermodynamics
D002412:Cations; D013463:Sulfuric Acid Esters; D008697:Methane