Geometrically constrained phosphorus ligands at the frontier between organometallic catalysis and molecular machines

Transition metal catalysis has a transformative impact on society, playing a crucial role in the production of modern materials, medicines, fuels, and chemicals. Phosphines have proved to be ideal ligands for a large number of transition-metal catalysed transformations such as cross-coupling, hydrogenation, carbonylation, metathesis, and alkene polymerisation.
The widespread applications of phosphine ligands in catalysis lies in their ability to stabilise metals in several oxidation states and geometries, and more recently, phosphine-metal complexes are increasingly used for the design of artificial molecular machines.
Caged phosphines, such as those developed in 2021 in the group of Prof. Berionni at UNamur have their phosphorus atom at the bridgehead of a cyclic cage can exhibit excellent control of the steric and electronic properties opening the possibility to use them for a large range of applications in a vast number of catalytic processes.