The Kinetic Order of an Interfacial Diels–Alder Reaction Depends on the Environment of the Immobilized Dienophile

Abstract

Cyclic voltammetry has been used to study the kinetics of the Diels–Alder reaction of cyclopentadiene with quinone immobilized on a monolayer (see scheme). By monitoring the reduction in current as the redox-active quinone is converted into the redox-inactive adduct, the reaction was shown to proceed with a second-order rate constant when hydroxyl groups were incorporated into the monolayer (X=OH), but with a first-order rate constant when methyl groups were incorporated (X=CH3).