Abstract by Ryan Carlsen
Chemistry and Biochemistry
DFT and Direct Dynamics of Cyclopentadiene-Tetrafluoroethylene Cycloaddition
Cycloaddition of cyclopentadiene and tetrafluoroethylene froms a mixture of 6,6,7,7-tetrafluorobicyclo[3.2.0]hept-2-ene ([2+2] cycloadduct) and 5,5,6,6-tetrafluorobicyclo[2.2.1]hept-2-ene ([4+2] cycloadduct). Spin-projected DFt calculations performed at the M062x/Def2TZVP level suggest competition between concerted and diradical pathways. The diradical pathway is complex and can lead to both [2+2]and [4+2] cycloadducts. Direct dynamics calculations show that some intermediates are skipped, but dynamics do not significantly alter reaction selectivity. Experiments measured the [2+2] to [4+2] product ration to verify our predictions.