Concerted [4 + 2] and Stepwise (2 + 2) Cycloadditions of Tetrafluoroethylene with Butadiene: DFT and DLPNO-UCCSD(T) Explorations

Abstract

Tetrafluoroethylene and butadiene form the 2 + 2 cycloadduct under kinetic control, but the Diels-Alder cycloadduct is formed under thermodynamic control. Borden and Getty showed that the preference for 2 + 2 cycloaddition is due to the necessity for syn-pyramidalization of the two CF2 groups in the 4 + 2 transition state. We have explored the full potential energy surface for the concerted and stepwise reactions of tetrafluoroethylene and butadiene with density functional theory, DFT (B3LYP and M06-2X), DLPNO-UCCSD(T), and CASSCF-NEVPT2 methods and with the distortion/interaction-activation strain model to explain the energetics of different pathways. The 2 + 2 cycloadduct is formed by an anti-transition state followed by two rotations and a final bond formation transition state. Energetics are compared to the reaction of maleic anhydride and ethylene.