Kinetic and energetic analysis of the free electron transfer

In this paper, the bimolecular free (unhindered) electron transfer (FET) from various trityl-containing compounds to the solvent radical cations of n-BuCl is described. In good agreement with the previously studied cases, the FET involving trityl-derived compounds results in the formation of two different types of the radical cation, which undergo the subsequent fragmentation via two alternative reaction channels. This unusual effect is caused by the intramolecular rotational motion in the ground-state molecules around the arrow-marked bond Ar-//-X-CPh 3 (Ar = aromatic moiety; X = S, O, NH, CH 2), since such oscillations are directly connected with the electron distribution within the molecule. An unhindered electron jump from the donor trityl compound to the solvent radical cation, taking place in the subfemtosecond time range, generates the solute radical cation with the inherited geometry and the electron distribution of its precursor. Among the whole variety of produced radical cations, two extreme conformer states can be distinguished, namely, a planar and a twisted state. The planar type represents the structures with minimum energy, whereas the twisted type is destabilized by the increased value of the rotational barrier in the ionized state. The difference in the energetic profiles between planar and twisted radical cations plays a crucial role in their subsequent fragmentation. The planar radical cation follows the thermodynamically favored pathway generating ArX (*) and Ph 3C (+). A distinct part of the twisted radical cation dissociates faster than it relaxes into the more preferable planar conformation and, therefore, produces a thermodynamically unfavorable couple of products: ArX (+) and Ph 3C (*). This fragmentation channel is exclusively caused by FET. The undertaken quantum chemical calculations enable the judgment of the energetics of the different dissociation channels of the radical cations of the trityl derivatives.