New publication of CIEl team : “Insights into the radical-radical and radical-substrate dimerization processes for substituted phenylmethylenepyrans“
Laurianne Wojcik, Isidoro Lopez, Sébastien Gauthier, Nolwenn Cabon, Pascal Le Poul,
Frédéric Gloaguen, Nicolas Le Poul
Electrochim. Acta 2019, 305, 304-311, DOI: 10.1016/j.electacta.2019.03.046
The electrochemically-induced C-C bond making/breaking for six differently R-substituted phenylmethylenepyrans has been investigated by voltammetry in organic media. All compounds display an irreversible oxidation peak whose potential is fully dependent on the electrophilic property of the substituent R. According to the voltammetric analysis, the mechanistic pathway, radical-radical or radical-substrate, for the intermolecular dimerization is fully R-dependent. Electronic structure calculations show that the spin population in the radical cation and the strength of the s-s C-C bond in the dimer strongly depend on the nature of R.