title: Solvatomagnetic Comparison Method: A Proper Quantification of Solvent Hydrogen-Bond Basicity.
abstract: The hydrogen-bond-acceptor basicity of an important class of solvents, the amphiprotic solvents (water, alcohols, primary and secondary amides, and carboxylic acids), has not yet been properly parametrized. In this work, the first scale of solvent hydrogen-bond basicity applicable to amphiprotic solvents is established by means of a new method that compares the19F NMR chemical shifts of 4-fluorophenol and 4-fluoroanisole in hydrogen-bond-acceptor solvents. This so-called solvatomagnetic comparison method is free of the shortcomings of the solvatochromic comparison method used so far and is easier to carry out than the pure base calorimetric method. The validity of the new scale is assessed by good linear correlations with spectroscopic, thermodynamic, and kinetic solute properties depending on the solvent hydrogen-bond basicity. In such correlation analysis of solvent effects on physicochemical properties, solvent and solute hydrogen-bond basicity scales must not be mixed, since it is shown here that solute and solvent scales are not equivalent. A comprehensive collection of parameters quantifying the hydrogen-bond basicity is presented for 168 solvents.
authors.affiliation: Université de Nantes , Laboratoire CEISAM, UMR 6230 CNRS, 2 rue de la Houssinière, 44322 Nantes, France.
authors.forename: Christian
authors.initials: C
authors.lastname: Laurence
authors.affiliation: Normandie Université , Laboratoire COBRA, UMR 6014 CNRS, 1 rue Lucien Tesnière, 76821 Mont-Saint-Aignan, France.
authors.forename: Julien
authors.initials: J
authors.lastname: Legros
authors.affiliation: Université de Nantes , Laboratoire CEISAM, UMR 6230 CNRS, 2 rue de la Houssinière, 44322 Nantes, France.
authors.forename: Pierre
authors.initials: P
authors.lastname: Nicolet
authors.affiliation: Normandie Université , INSA de Rouen, UMR 6270 CNRS, Avenue de l'Université, 76801 Saint-Etienne du Rouvray, France.
authors.forename: Daniela
authors.initials: D
authors.lastname: Vuluga
authors.affiliation: Université de Nantes , Laboratoire CEISAM, UMR 6230 CNRS, 2 rue de la Houssinière, 44322 Nantes, France.
authors.forename: Agisilaos
authors.initials: A
authors.lastname: Chantzis
authors.affiliation: Université de Nantes , Laboratoire CEISAM, UMR 6230 CNRS, 2 rue de la Houssinière, 44322 Nantes, France.|Institut Universitaire de France (IUF) , 103 Boulevard Saint-Michel, 75005 Paris, France.
authors.forename: Denis
authors.initials: D
authors.lastname: Jacquemin