Understanding the enhanced reactivity of strained intramolecular Frustrated Lewis Pairs

Abstract

The poorly understood factors controlling the enhanced reactivity of strained intramolecular frustrated Lewis pairs (FLPs) having a rigid biphenylene tether have been quantitatively explored in detail by means of computational methods. With the help of the activation strain model of reactivity and the energy decomposition analysis methods, the challenging allene activation reaction has been selected and compared to the analogous process mediated by a related intramolecular FLP having a more flexible tether, which is significantly less reactive. In addition, the influence of the nature of the Lewis acid atom on the reactivity of the strained FLP has been considered as well showing that the reactivity steadily decreases when going down in group 13.