Anion Complexation Strongly Influences the Reactivity of Octafluorocyclooctatetraene

Six stationary points (three minima and three TS) in the thermal energy profile of octafluorocyclooctatetraene (F-8-COT) have been explored. The TSs corresponding to the inversion process of F-8-COT and its transformation in perfluoro bicyclo[2.2.2]octa-2,5,7-triene (F-8-BOT) and subsequent to perfluoro tetracyclo[4.2.0.02.0(2,8),0(5,7)]octene (F-8-TCO) have been characterized. The results have been compared to the energy profile in the parent compound (cyclooctatetraene or COT). In addition, the effect of the formation of anion-pi complexes in the reaction profile has been explored. The results have been rationalized using the electrostatic potential of the isolated stationary points and thermodynamic cycles involving the complex formation in the minima and TS and the barriers in the isolated molecules. Moreover, the electron density has been analyzed with the AIM methodology.

Automated summary

Six stationary points in the thermal energy profile of F-8-COT were explored, including three minima and three transition states corresponding to its transformation into F-8-BOT and F-8-TCO. The formation of anion-pi complexes in the reaction profile was investigated, and the results were rationalized using electrostatic potential and thermodynamic cycles. Additionally, electron density analysis was conducted using the AIM methodology.