Phosphines and other P(III)‐derivatives with Cavity‐shaped Subunits: Valuable Ligands for Supramolecular Metal Catalysis, Metal Confinement and Subtle Steric Control

Abstract

AbstractTertiary phosphines and other P(III)‐derivatives are the par excellence ligands in industrially relevant homogeneous catalysis. A promising, recent development in this field concerns the use of P(III)‐compounds that incorporate cavity‐shaped subunits capable of assisting metal‐centred reactions, either by functioning as receptor moieties, creating confinement about the reactive centre or merely by influencing main catalytic steps via strong steric interactions exerted on the metal first coordination sphere. This Minireview, which is based on selected examples, illustrates the utility of covalently‐constructed phosphines that incorporate a cavity and highlights future directions that deserve development in ligand design.