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

Abstract : 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.