Proton Transfer Reactions of Triazol-3-ylidenes: Kinetic Acidities and Carbon Acid pKa Values for Twenty Triazolium Salts in Aqueous Solution

Massey, R.S.; Collett, C.J.; Lindsay, A.G.; Smith, A.D.; O'Donoghue, A.C.

Abstract

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.

Citation

Massey, R., Collett, C., Lindsay, A., Smith, A., & O'Donoghue, A. (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. https://doi.org/10.1021/ja308420c

• Journal Article Type: Article
• Publication Date: Dec 19, 2012
• Deposit Date: May 16, 2013
• Publicly Available Date: Feb 15, 2016
• Journal: Journal of the American Chemical Society
• Print ISSN: 0002-7863
• Electronic ISSN: 1520-5126
• Publisher: American Chemical Society
• Peer Reviewed: Peer Reviewed
• Volume: 134
• Issue: 50
• Pages: 20421-20432
• DOI: https://doi.org/10.1021/ja308420c
• Public URL: https://durham-repository.worktribe.com/output/1484279