Kinetics of the Isomerization of Quadricyclane to Norbornadiene Promoted by Tin(II) Chloride and Palladium(II) Chloride

Article abstract of DOI:10.1021/jo00185a018

The conversion of quadricyclane to norbornadiene is promoted by both SnCl2 and PdCl2.The SnCl2 reaction occurs by a second-order process with activation parameters of ΔG(excit.), ΔH(excit.), and ΔS(excit.) of 22.5 kcal/mol, 13.9 kcal/mol, and -28.7 eu, respectively.The PdCl2-promoted reaction occurs by formation of an equilibrium species and follows Michaelis-Menton kinetics.A theoretical interpretation based on the Dewar-Duncanson model of bonding of metal ions with olefins is used to describe possible mechanistic differences in the reactions.