Abstract
[CH 3SO 2] +, [CH 3SO 3H 2] + and [CH 3SO 2OCH 3H] +, 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 −1 has been obtained for methanesulfonic acid by the bracketing procedure, but the site of proton attachment in [CH 3SO 3H 2] + ions could not be established, either by CID or kinetic evidence. The methylation of SO 2 by (CH 3) 2F + ions has been ascertained to yield [CH 3SO 2] + ions methylated on oxygen, in analogy to the same reaction observed in a superacid medium.
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