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Durham University

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Publication details for Prof. AnnMarie C. O'Donoghue

Massey, R.S., Collett, C.J., Lindsay, A.G., Smith, A.D. & O'Donoghue, A.C. (2012). Proton Transfer Reactions of Triazol-3-ylidenes: Kinetic Acidities and Carbon Acid pKa Values for Twenty Triazolium Salts in Aqueous Solution. Journal of the American Chemical Society 134(50): 20421-20432.

Author(s) from Durham


Second-order rate constants have been determined for deuteroxide ion-catalyzed exchange of the C(3)-proton for deuterium, kDO (M–1 s–1), of a series of 20 triazolium salts in aqueous solution at 25 °C and ionic strength I = 1.0 (KCl). Evidence is presented that the rate constant for the reverse protonation of the triazol-3-ylidenes by solvent water is close to that for dielectric relaxation of solvent (1011 s–1). These data enabled the calculation of carbon acid pKa values in the range 16.5–18.5 for the 20 triazolium salts. pD rate profiles for deuterium exchange of the triazolium salts reveal that protonation at nitrogen to give dicationic triazolium species occurs under acidic conditions, with estimates of pKaN1 = −0.2 to 0.5.