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

Dennis Svatunek | Zendy; Ryan P. Pemberton | Zendy; Joel L. Mackey | Zendy; Peng Liu | Zendy; K. N. Houk | Zendy

Open Access

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

Author(s) -

Dennis Svatunek,

Ryan P. Pemberton,

Joel L. Mackey,

Peng Liu,

K. N. Houk

Publication year - 2020

Publication title -

the journal of organic chemistry

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 1.2

H-Index - 228

eISSN - 1520-6904

pISSN - 0022-3263

DOI - 10.1021/acs.joc.0c00222

Subject(s) - tetrafluoroethylene , chemistry , cycloaddition , transition state , kinetic control , maleic anhydride , computational chemistry , density functional theory , isomerization , potential energy surface , kinetic energy , photochemistry , organic chemistry , molecule , catalysis , physics , quantum mechanics , polymer , copolymer

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 CF 2 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.

The content you want is available to Zendy users.

Already have an account? Click here to sign in.

Having issues? You can contact us here

Accelerating Research