title: Gutmann's Donor Numbers Correctly Assess the Effect of the Solvent on the Kinetics of SN Ar Reactions in Ionic Liquids.
abstract: We report an experimental study on the effect of solvents on the model SN Ar reaction between 1-chloro-2,4-dinitrobenzene and morpholine in a series of pure ionic liquids (IL). A significant catalytic effect is observed with reference to the same reaction run in water, acetonitrile, and other conventional solvents. The series of IL considered include the anions, NTf2 (-) , DCN(-) , SCN(-) , CF3 SO3 (-) , PF6 (-) , and FAP(-) with the series of cations 1-butyl-3-methyl-imidazolium ([BMIM](+) ), 1-ethyl-3-methyl-imidazolium ([EMIM](+) ), 1-butyl-2,3-dimethyl-imidazolium ([BM2 IM](+) ), and 1-butyl-1-methyl-pyrrolidinium ([BMPyr](+) ). The observed solvent effects can be attributed to an "anion effect". The anion effect appears related to the anion size (polarizability) and their hydrogen-bonding (HB) abilities to the substrate. These results have been confirmed by performing a comparison of the rate constants with Gutmann's donicity numbers (DNs). The good correlation between rate constants and DN emphasizes the major role of charge transfer from the anion to the substrate.
authors: Departamento de Química, Facultad de Ciencias, Universidad de Chile, Casilla, 653, Santiago, Chile. jazminalarcon@ug.uchile.cl.
authors: Jazmín
authors: J
authors: Alarcón-Espósito
authors: Departamento de Química, Facultad de Ciencias, Universidad de Chile, Casilla, 653, Santiago, Chile.
authors: Renato
authors: R
authors: Contreras
authors: Facultad de Química, Pontificia Universidad Católica de Chile, Código Postal, 7820436, Santiago, Chile.
authors: Ricardo A
authors: RA
authors: Tapia
authors: Centro de Química Médica, Facultad de Medicina, Clínica Alemana Universidad del Desarrollo, Código Postal, 771-0162, Santiago, Chile.
authors: Paola R
authors: PR
authors: Campodónico
keywords: Gutmann's donicity numbers; Lewis acidity/basicity; anion (solvent) effects; ionic liquids