Steric Crowding Makes Challenging Csp3–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–Csp3+ complexes, the more efficient the fluorination, seemingly a result of sterically accelerated C–F reductive elimination along with simultaneous deceleration of its competing processes (β-H elimination).