Steric Crowding Makes Challenging C(sp3)-F Reductive Eliminations Feasible.

A high-yielding fluorination of (triphos)Pt-R+ has been achieved using an array of F+ sources, with XeF2 yielding R-F in minutes. The C-F coupling proved to be a stereoretentive process that proceeds via a concerted reductive elimination from a putative dicationic Pt(IV) center. The larger the steric congestion of the (triphos)Pt-C-sp3(+) complexes, the more efficient the fluorination, seemingly a result of sterically accelerated C-F reductive elimination along with simultaneous deceleration of its competing processes (beta-H elimination).