Encapsulation of Azaphosphatranes and Proazaphosphatranes in Confined Spaces

Proazaphosphatranes (also named Verkade's superbases) and their azaphosphatrane conjugated acids have been recently been shown to be confined in either covalent or self-assembled molecular cages, or immobilized in nanopores of hybrid materials. The encapsulation of these phosphorus moieties turns out to strongly affect both their acid-base, catalytic, and recognition properties. The thermodynamics and kinetics of the proton transfer as well as the selectivity and catalytic activities of Verkade's superbases were strongly changed upon their confinement in a hemicryptophane cavity. Moreover, self-assembled cages, including azaphosphatrane moieties, were found to display remarkable anion recognition properties in water. In this Minireview, these new aspects of the chemistry of aza- and proaza-phosphatranes are presented, in order to highlight the great potential of such an approach.