Nevertheless, according to TA measurements, in the presence of toluene, a delayedsinglet excited state of the Sc 3+ complex (with oxygen involved) seems to be responsible for the productive reaction pathway that undergoes SET from toluene during the production of a toluene radical and the Sc 3+ -O2 •-complex, as verified by the eight-line EPR spectrum arising from the I = 7/2 45 Sc nucleus. Subsequently, the superoxide ion, O2 •-abstracts a proton from the benzyl radical cation to produce a hydroperoxy radical, HOO • and a benzyl radical. Subsequently, the interaction between the benzyl radical and O2 produces the peroxyl radical, followed by benzaldehyde formation. Further oxidation of benzaldehyde yields the desired product, benzoic acid (2a), as well as H2O2, as confirmed by iodometry (see Supporting Section S9 for details). Alternatively, the aryl radical cation can react with a cyanide source (TMSCN) to generate a cyclopentadienyl radical and produce a cyanoarene by hydrogen transfer. The final transformation using the hydroperoxy radical is likely the one proposed by Nicewicz but an alternative participation of oxygen is not excluded.