The enormous acidifying effect of the supersubstituent ᎐ ᎐ NSO 2 CF 3 on the acidity of derivatives of benzenesulfonamide and toluene-p- sulfonamide in the gas phase and in dimethyl sulfoxide
The effect of stepwise replacement of ᎐ ᎐ O oxygen atoms by ᎐ ᎐ NSO 2 CF 3 fragments in the sulfonyl group of toluenep-sulfonamide and benzenesulfonamide on their acidity has been studied in the gas phase and dimethyl sulfoxide (DMSO). Incorporation of the first ᎐ ᎐ NSO 2 CF 3 group into 4-MeC 6 H 4 SO 2 NH 2 increases its gas-phase acidity by 23.6 kcal mol Ϫ1 . Substituting the second ᎐ ᎐ O by the ᎐ ᎐ NSO 2 CF 3 group leads to an additional acidity increase of 10.7 kcal mol Ϫ1 ; the total acidity increase is thus 34.3 kcal mol Ϫ1 (25 powers of ten!). In DMSO solution the total acidity increase is 13 pK a units (17.7 kcal mol Ϫ1 ). These findings are also supported by computational studies using DFT B3LYP at the 6-31ϩG* level and the semiempirical PM3 method. The results of this work have potentially important implications for the design of new strongly acidic catalytic materials
