The novel -diketo compound (3-acetyl-4-oxopentanoic acid) OPAA is here synthesized, completely characterized in the solid state by means of X-ray crystallography and in solution by potentiometry and 1H and 13C NMR spectroscopy. In the solid state, OPAA exhibits the di-keto (DK) structure, while in solution a strongly solvent dependent tautomeric equilibrium is observed. Theoretical ab-initio calculations employing DFT at B3LYP/6-311G** level and different methods of theoretical model chemistry (CBS-4M, G3MP2, CBS-QB3) are used to extensively investigate the tautomeric equilibrium in comparison with experimental data. Solvent effects are evaluated using CPCM continuum solvation method; among all implied methods, CBS-4M is the one that better predicts experimental data and is able to qualitatively describe tautomeric equilibrium in solution, allowing thermodynamic calculation of pKa. Furthermore a supermolecular solvent approach is used to better analyze solvent-solute interactions in order to forecast chemical properties.

Solvent effect on keto-enol tautomerism in a new B-diketone: a comparison between experimental data and different theoretical approaches / Ferrari, Erika; Saladini, Monica; Pignedoli, Francesca; Spagnolo, Ferdinando; Benassi, Rois. - In: NEW JOURNAL OF CHEMISTRY. - ISSN 1144-0546. - STAMPA. - 35:(2011), pp. 2840-2847. [10.1039/c1nj20576e]

Solvent effect on keto-enol tautomerism in a new B-diketone: a comparison between experimental data and different theoretical approaches.

FERRARI, Erika;SALADINI, Monica;BENASSI, Rois
2011

Abstract

The novel -diketo compound (3-acetyl-4-oxopentanoic acid) OPAA is here synthesized, completely characterized in the solid state by means of X-ray crystallography and in solution by potentiometry and 1H and 13C NMR spectroscopy. In the solid state, OPAA exhibits the di-keto (DK) structure, while in solution a strongly solvent dependent tautomeric equilibrium is observed. Theoretical ab-initio calculations employing DFT at B3LYP/6-311G** level and different methods of theoretical model chemistry (CBS-4M, G3MP2, CBS-QB3) are used to extensively investigate the tautomeric equilibrium in comparison with experimental data. Solvent effects are evaluated using CPCM continuum solvation method; among all implied methods, CBS-4M is the one that better predicts experimental data and is able to qualitatively describe tautomeric equilibrium in solution, allowing thermodynamic calculation of pKa. Furthermore a supermolecular solvent approach is used to better analyze solvent-solute interactions in order to forecast chemical properties.
35
2840
2847
Solvent effect on keto-enol tautomerism in a new B-diketone: a comparison between experimental data and different theoretical approaches / Ferrari, Erika; Saladini, Monica; Pignedoli, Francesca; Spagnolo, Ferdinando; Benassi, Rois. - In: NEW JOURNAL OF CHEMISTRY. - ISSN 1144-0546. - STAMPA. - 35:(2011), pp. 2840-2847. [10.1039/c1nj20576e]
Ferrari, Erika; Saladini, Monica; Pignedoli, Francesca; Spagnolo, Ferdinando; Benassi, Rois
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11380/695883
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