C-F→Ln/An interactions in synthetic f-element chemistry

The coordination of C-F moieties to electrophilic metal cations has been increasingly recognized in f-element chemistry over the last two decades. These C-F -> Ln/An interactions are readily identified in the solid state and can persist in solution. The binding energies of C-F -> Ln/An interactions lead to their ready displacement to expose metal centers to substrates, which is implicated in cationic polymerization catalysts. C-F -> Ln/An coordination is also an elementary step in C-F bond activation, proceeding through either homolytic or heterolytic cleavage of chemically inert C-F bonds. The influence of C-F -> Ln/An interactions on the geometries of coordination compounds and their electronic impact on metal cations are also examined in this Perspective article.