Correlation of Structures and Solvent Properties of Ionic Liquids

The aim of the thesis was to find out a correlation between the structural properties of ionic liquids and their influence on organic reactivity. Kinetic studies were performed on nucleophilic substitutions (Menschutkin reaction and dediazonation, Chapter 1) and Diels-Alder reactions (Chapter 2). Data obtained, together with ab-initio calculations, confirm an active role of the hydrogen bond interaction between ionic liquid and substrates/ activated complex in the influence of the reactivity. In the dediazonation reactions, competition between the scarce nucleophilic [Tf2N]? anion and bromide, surprisingly bears to the formation of the incorporating products with [Tf2N]? only (section 1.2.2). ESI-MS experiments on pure and mixed ionic liquids were performed in order to understand the inner interactions responsible for this peculiar behaviour (section 1.2.3). In order to better elucidate the structural features responsible of the physical properties of ionic liquids, two computer aided approaches were used in this thesis: prediction of the melting point of a class of pyridinium substituted ionic liquids using a recursive neural network model (Chapter 3) and calculation of the physical properties of [bmim][PF6] and [bmim][BF4] through molecular dynamic simulations (Chapter 4).