Anionic phosph(in)ito (“phosphoryl”) ligands: Non-classical “actor” phosphane-type ligands in coordination chemistry

•Transition metal complexes with κ1-Pmetalated ligands of general formula {P(O)R1R2}.•Electronic properties of O-anionic κ1-P(III)-phosph(in)ito ligands {P(O−)R1R2}.•Main prevalent activities of metal complexes with κ1-Pmetalated ligands {P(O)R1R2}.

This contribution gives an overview of transition metal complexes with κ1-Pmetalated organophosphorus ligands of general formula {R1R2P(O)}. Their preparation is achieved via a wide range of synthetic pathways. Recent experimental and theoretical studies reported on O-anionic κ1-Pphosph(in)ite complexes revealed that O-anionic κ1-Pphosph(in)ito ligands {R1R2P(O−)} can be classified as electron donating P(III)phosphane-type ligands which may outclass carbene ligands in term of net electronic donation. The promising results obtained in catalysis with these “non-classical” actor ligands pave the way for future investigations in challenging organic chemical transformations. In view of their electron donating properties and their ability to interact with donor hydrogen atom for supramolecular structure formations, O-anionic κ1-Pphosph(in)ito ligands have still long way to go in transition metal chemistry.

Graphical abstractMono- and bi-dentate O-anionic κ1-P(III)-phosph(in)ite complexes.Figure optionsDownload full-size imageDownload high-quality image (51 K)Download as PowerPoint slide