SOLVENT EFFECTS OF KINETICS OF [1,5] H-SHIFT IN CYCLOPENTADIENE AND ITS DERIVATIVES

Abstract

Geometries of reactants, products (in the case of fluoro derivatives), and transition states in gas and solution phases of [1,5] H-shift of cyclopentadiene and 2-fluorocyclo-pentadiene were optimized using B3LYP/6-31++G(d,p) . The solvent effects were included using the Polarizable Continuum Model (PCM). Four solvent systems i.e. chloroform, dichloromethane, diethylether, and methanol, were considered. For cyclopentadiene, single point MP2/6-31++G(d,p) were also carried out. For cyclopentadiene and 2-fluorocyclopentadiene, using B3LYP/6-31++G(d,p) activation free energies of 25.47 and 28.74 kcal/mol respectively were yielded for the reaction in vacuum. In solutions, calculated activation energies for the reaction are slightly decreased with the reduction of around 0.5–3 kcal/mol depending on solvent. Good correlation between the solvent polarity and activation energies was also observed. Thus, the [1.5] H-shift in cyclopentadiene and its derivatives could be enhanced in polar solvents.