Filling a niche in “ligand space” with bulky, electron-poor phosphorus (III) alkoxides

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 PRn(ORF)3-n, where R = Ph, RF = C(H)(CF3)2 and C(CF3)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

Synthesis and complexation of heptafluoroisopropyldiphenylphosphine

We report a one-step synthesis of the phosphine, PPh2iC3F7 from commercially available precursors. The stereoelectronic properties of the phosphine were probed by coordination to transition metals. Mo(CO)5PPh2iC3F7 was synthesised and the synthesis and structure of trans-PtCl2(PPh2iC3F7)2 are described. PPh2iC3F7 was found to be a bulky electron-withdrawing ligand