# Oxidative Addition of C‐F Bonds to the Phosphoranide Ion [P(C2F5)2F2]−

## TL;DR

This paper reports a new method for breaking strong C-F bonds using a phosphoranide ion, enabling the functionalization of fluorinated compounds under mild conditions.

## Contribution

The first anionic P(III) species capable of oxidative addition to C-F bonds is presented.

## Key findings

- The [P(C2F5)2F2]− anion reacts with fluorinated arenes, olefins, and acid fluorides to form hexacoordinated P(V) phosphates.
- The resulting trifluorophosphates are colorless, thermally stable, and bench stable.
- This method expands the tools available for functionalizing strong C-F bonds.

## Abstract

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.

The difluorobis(pentafluoroethyl)phosphoranide anion (λ
4
σ
4‐phosphate) reacts with substrates containing activated C─F bonds (R
f  =  perfluoroaryl, ‐alkenyl, and ‐acetyl) yielding corresponding trifluorophoshates. The colorless solids exhibit a high thermal stability and are bench stable. This reaction behavior extends the toolbox for possible functionalization of inherently strong C─F bonds.