Solvatochromic correlation analysis of monomolecular SN1/E1 heterolysis reactions of tertiary haloalkanes

Abstract A solvatochromic analysis of the reaction of the solvent-dependent heterolysis reaction of tertiary haloalkanes, based on the properties of the solvents used, allows visualizing and interpreting the intermolecular solute/solvent interactions that control these important chemical processes. The results achieved confirm that the rate of these chemical processes increases in a balanced way with an increase in the polarizability, the dipolarity, and the hydrogen-bond donor (HBD) acidity of the solvents, and to a much lesser extent with their their hydrogen-bond acceptor (HBA) basicity. Contrary to what is currently accepted, namely that the rate of these processes is not or is negatively affected by the solvent's HBA basicity (nucleophilicity), we conclude that if it does, it is positively affected. We also conclude that the Gibbs activation energy of the heterolysis of 2-chloro-2-methylpropane (t-BuCl) decreases by the four solvatochromic contributions to the overall intermolecular solute/solvent interactions.