Filling a Niche in “Ligand Space” with Bulky, Electron‐Poor Phosphorus(III) Alkoxides

Abstract

Abstract The chemistry of phosphorus(III) ligands, which are of key importance in coordination chemistry, organometallic chemistry and catalysis, is dominated by relatively electron‐rich species. Many of the electron‐poor P III ligands that are readily available have relatively small steric profiles. As such, there is a significant gap in “ligand space” where more sterically bulky, electron‐poor P III ligands are needed. This contribution discusses the coordination chemistry, steric and electronic properties of P III ligands bearing highly fluorinated alkoxide groups of the general form PR n (OR F ) 3− n , where R=Ph, R F =C(H)(CF 3 ) 2 and C(CF 3 ) 3 ; n= 1–3. These ligands are simple to synthesize and a range of experimental and theoretical methods suggest that their steric and electronic properties can be “tuned” by modification of their substituents, making them excellent candidates for large, electron‐poor ligands.