The electronic structure of the known intermediates of perfluoroolefins was analyzed from the standpoint of thermal electronic excitations. The calculated (ab initioDZ) energies of the perpendicular triplet state T1 of the perfluorolefins are compared with the experimental enthalpies of formation of the intermediates. A new mechanism of cyclodimerization of tetrafluoroethylene is proposed, including its thermal excitation into the lowest triplet state as the limiting stage.
Russian Journal of Applied Chemistry – Springer Journals
Published: Oct 13, 2004
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