[CH3SO2]+, [CH3SO3H2]+and [CH3SO2OCH3H]+, positive even-electron ions from hexavalent sulfur compounds, have been studied by Fourier transform ion cyclotron resonance and collision-induced dissociation (CID). These ions showed no evidence of undergoing S → O methyl group shift, at variance with easy skeletal rearrangements frequently postulated for ionized sulfones and sulfonyl derivatives. A proton affinity value of 184 ± 2 kcal mol-1has been obtained for methanesulfonic acid by the bracketing procedure, but the site of proton attachment in [CH3SO3H2]+ions could not be established, either by CID or kinetic evidence. The methylation of SO2by (CH3)2F+ions has been ascertained to yield [CH3SO2]+ions methylated on oxygen, in analogy to the same reaction observed in a superacid medium. © 1992.
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