Concerted proton electron transfer or hydrogen atom transfer? an unequivocal strategy to discriminate these mechanisms in model systems

Concerted proton electron transfer (CPET) and hydrogen atom transfer (HAT) are two important mechanisms in many fields of chemistry, which are characterized by the transfer of one proton and one electron. The distinction between these mechanisms may be challenging in several reactions; thus, different computational methods have been developed for this purpose. In this work, we present a computational strategy to distinguish the two mechanisms, rationalizing the factors controlling the reactivity in four different model reactions. Fist, the transition state SOMO (singly occupied molecular orbital) is visualized, presenting all the limits and ambiguities of this analysis. Then, the electron flow along the reaction path is evaluated through the intrinsic bond orbitals (IBOs); this analysis allows to describe correctly the mechanism of each reaction in agreement with previous studies. Furthermore, some structural modifications are applied to the transition state of each system and the energetic differences are rationalized in the framework of the activation strain analysis to understand the geometrical and electronic factors governing the reactivity and the selection of CPET or HAT mechanism. Lastly, the effect of the donor-acceptor distance is evaluated. It emerges that a combined computational analysis is crucial to understand not only the distinction between the two mechanisms, but also the molecular reasons why one mechanism is operative in a specific reaction.