Isomerization of the Dimethyl Sulfoxide Radical Cation and the Possible Analogies to the Neutral Speciices

Article abstract of DOI:10.1021/ja00228a016

The interconvertibility of the dimethyl sulfoxide (DMSO) radical cation, its proton tautomeric aci-DMSO, and methyl methanesulfenate isomers, respectively, has been investigated by application of collision activation mass spectrometry and metastable ion studies.The isomerization reactions are discussed based on isotopic labeling studies as well as thermodynamical considerations.The interconvertibility of the radical cations of DMSO and aci-DMSO as well as the isomerization of the methyl methanesulfenate radical cation into the radical cation of DMSO could be concluded, whereas no unambiguous evidence concerning in possible operation of the DMSO to methyl methanesulfenate isomerization was obtained.Low-pressure gas-phase pyrolysis studies have been applied to elucidate the possible analogies to the corresponding neutral species.