The acid-base properties of selected derivatives of the [1,2,4]triazolo[3,2-c][1,2,4]triazole fused aromatic system have been investigated by UV–vis spectroscopy. Neutral heterobicycles (HL) exhibit amphoteric behavior (they can deliver the N–H proton forming the conjugated base L- and can accept up to two protons, forming the species H2L+ and H3L++) and show an unprecedented tautomeric switching upon protonation, as revealed by single crystal X-ray analysis and confirmed by theoretical calculations. By varying the groups attached at the heterocycle, a remarkable shift of pKai values, up to 5–6 units, is observed. In particular, with strong electron attractor groups at position 7 (e.g. p-nitrophenyl or pentafluorophenyl) the neutral compounds are stronger acids than phenol or p-nitrophenol.

Proton induced tautomeric switching in N-rich aromatics with tunable acid-base character

CENTORE, ROBERTO;MANFREDI, CARLA;FUSCO, SANDRA;MAGLIONE, CIRA;CARELLA, ANTONIO;
2015

Abstract

The acid-base properties of selected derivatives of the [1,2,4]triazolo[3,2-c][1,2,4]triazole fused aromatic system have been investigated by UV–vis spectroscopy. Neutral heterobicycles (HL) exhibit amphoteric behavior (they can deliver the N–H proton forming the conjugated base L- and can accept up to two protons, forming the species H2L+ and H3L++) and show an unprecedented tautomeric switching upon protonation, as revealed by single crystal X-ray analysis and confirmed by theoretical calculations. By varying the groups attached at the heterocycle, a remarkable shift of pKai values, up to 5–6 units, is observed. In particular, with strong electron attractor groups at position 7 (e.g. p-nitrophenyl or pentafluorophenyl) the neutral compounds are stronger acids than phenol or p-nitrophenol.
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11588/608274
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