The elusive dimethylhydroxysulfuranyl radical. An intermediate or a transition state?

Abstract

The stability and dissociations of dimethylhydroxysulfuranyl radical, a key intermediate in the atmospheric oxidation of dimethyl sulfide, have been investigated by neutralization-reionization mass spectrometry and ab initio calculations. Dimethylhydroxysulfuranyl radical (1) and its d 6 derivative 2 were generated in the gas phase by neutralization of protonated dimethylsulfoxide and dimethylsulfoxide-d 6 , respectively. Hypervalent radical 1 dissociates completely within 4.5 μs to CH 3 SOH by loss of CH 3 . and to (CH 3 ) 2 S by loss of OH .