This work provides ail in-depth look at the bimolecular free-electron transfer (FET) from bisubstituted (amine and -CR2SiMe3 groups) aromatic molecules to the solvent radical cations of n-BuCl Because of the low rotational barriers, the Substrates obtain all possible arrangements in solution. The electron jump is an unhindered process that does not require a defined encounter complex. The resulting radical cations show great conformer diversity because they directly inherit the geometry of their mobile precursors. One part of the radical cations is unstable and dissociates instantly, but the other one is metastable (microsecond lifetime). The two substituents reduce the barrier of internal rotation, resulting in stabilization of the otherwise good leaving group -SiMe3. The amine group governs the reactivity of the system because it receives most of the electron density of the fluctuating highest MOs: primary and secondary airline groups lead to both instant and delayed formation of aminyl radicals; tertiary amines cause the rapid loss of an alpha-H+ to yield alpha-aminoalkyl radicals.