New insights into coordination-cage based catalysis

This review article summarises work from the author's group on catalysis using coordination cages over the (approximate) period 2018-2024. Recent insights discussed include (i) the general mechanism of catalysis, which involves co-location of reaction partners using orthogonal interactions involving the cage cavity (neutral hydrophobic substrates) and the surface anion-based reaction partners; (ii) the role of the cage exterior surface in facilitating catalysis in some cases; (iii) quantitative analysis of anion-binding to the cage surface, as a complement to measurement of binding constants of neutral guests inside the cavity; (iv) a new type of redox-based catalysis using reactive oxygen species, which are generated by reaction of oxidants such as H 2 O 2 and HSO 5 − with Co( ii )/Co( iii ) redox couples in the cage superstructure. Collectively the results discussed provide signficant new possibilities for further exploration of catalysis using supramolecular assemblies. Recent work on catalysed reactions using coordination cage hosts, including new mechanistic insights and reactions types, is reviewed.