Oxidative Addition of C‐F Bonds to the Phosphoranide Ion [P(C ₂ F ₅ ) ₂ F ₂ ] ⁻

Oxidative additions of C─Hal bonds (Hal = F, Cl, Br, I) are widely known for a variety of transition metal complexes owing to their range of oxidation states and flexible coordination sphere. Low valent main group element compounds were shown to mimic this reaction behavior, due to the propensity of changing their oxidation state and coordination number by +2. Yet the addition to C─F bonds is especially challenging due to a large bond dissociation energy. While several examples are known for compounds from group 13 and 14, only few reports demonstrate this type of reaction for compounds from group 15. Herein we report the first anionic P(III) species undergoing an oxidative addition of C─F bonds. The tetracoordinated [P(C₂F₅)₂F₂]^--anion reacts readily with fluorinated arenes, olefins, and acid fluorides yielding respective hexacoordinated P(V) phosphates under mild conditions.