The chemistry of phosphines in constrained, well-defined microenvironments

Developments in the confinement of phosphines within micro- or nano-environments are explored. Phosphines are ubiquitous across metal coordination chemistry and underpin some of the most famous homogeneous transition metal catalysts. Constraining phosphines within confined environments influences not only their behaviour but also that of their metal complexes. Notable examples include the use of metal–organic frameworks (MOFs) or metal–organic cages (MOCs) to support phosphines which demonstrate how the microenvironment within such constructs leads to reactivity modification. The development of phosphine confinement is explored and parallels are drawn with related constrained macrocyclic systems and mechanically interlocked molecules. The review concludes by identifying areas that remain a challenge and those that will provide new avenues for research.