A Database of Dispersion-Induction DI, Electrostatic ES, and Hydrogen Bonding α1 and β1 Solvent Parameters and Some Applications to the Multiparameter Correlation Analysis of Solvent Effects

C. Laurence (1) , Julien Legros (2) , A. Chantzis (1) , A. Planchat (1) , D. Jacquemin (1)

1 CEISAM - Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation
2 COBRA - Chimie Organique et Bioorganique : Réactivité et Analyse

For about 300 solvents, we propose a database of new solvent parameters describing empirically solute/solvent interactions: DI for dispersion and induction, ES for electrostatic interactions between permanent multipoles, α1 for solute Lewis base/solvent Lewis acid interactions, and β1 for solute hydrogen-bond donor/solvent hydrogen-bond acceptor interactions. The main advantage over previous parametrizations is the easiness of extension of this database to newly designed solvents, since only three probes, the betaine dye 30, 4-fluorophenol, and 4-fluoroanisole are required. These parameters can be entered into the linear solvation energy relationship A = A0 + di(DI) + eES + aα1 + bβ1 to predict a large number of varied physicochemical properties A and to rationalize the multiple intermolecular forces at the origin of solvent effects through a simple examination of the sign and magnitude of regression coefficients di, e, a, and b. Such a rationalization is illustrated for conformational and tautomeric equilibria and is supported by quantum-mechanical calculations.

Domaines: Chimie

C. Laurence, Julien Legros, A. Chantzis, A. Planchat, D. Jacquemin. A Database of Dispersion-Induction DI, Electrostatic ES, and Hydrogen Bonding α1 and β1 Solvent Parameters and Some Applications to the Multiparameter Correlation Analysis of Solvent Effects. Journal of Physical Chemistry B, 2015, 119 (7), pp.3174-3184. ⟨10.1021/jp512372c⟩. ⟨hal-02046156⟩