Massey, R.S. and Collett, C.J. and Lindsay, A.G. and Smith, A.D. and 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). pp. 20421-20432.
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.
| Item Type: | Article |
|---|---|
| Full text: | (AM) Accepted Manuscript Download PDF (884Kb) |
| Status: | Peer-reviewed |
| Publisher Web site: | http://dx.doi.org/10.1021/ja308420c |
| Publisher statement: | This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://dx.doi.org/10.1021/ja308420c. |
| Date accepted: | No date available |
| Date deposited: | 15 February 2016 |
| Date of first online publication: | December 2012 |
| Date first made open access: | No date available |
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