Remarkable kinetic stability of -thiocarbamoyl substituted 4-methoxybenzylcations

4-Methoxybenzyl cations bearing -(N,N-dimethylcarbamoyl) and -(N,N-dimethylthiocarbamoyl) substituents have been generated photochemically upon irradiation of precursors with pentafluorobenzoate or 4-methoxybenzoate leaving groups. The ions have been observed with flash photolysis in 40:60 acetonitrile:water and in 50:50 methanol:water, and rate constants were measured for their decay in solvent alone and for their capture by azide ion. The cations so studied and their lifetimes in 40% acetonitrile are 6 , ArC + H-CONMe 2 , 0.6 s; 2 , ArC + H-CSNMe 2 , 7 ms; and 4 , ArC + (CH 3 )-CSMe 2, 6 ms, where Ar = 4-MeOC 6 H 4 . The cation 4 reacts with solvent by elimination of a proton from the -methyl group, and the rate constant for solvent addition must be less than 1 s -1 . The CSNMe 2 substituted cations are 10 5 -10 7 -fold longer lived than analogs where the thioamide group has been replaced with an -methyl. The UV-visible absorption spectra of these two cations also show significant differences from those of typical 4-methoxybenzyl cations. Thus, both the lifetimes and spectra point to a strong interaction of the benzylic centre with the thioamide group. Key words: flash photolysis, thiocarbamoyl stabilized carbocation, photosolvolysis.