General, Quantified Structure-Performance Correlations for Synergistic Heteronuclear Electro‑, Polymerization, and Asymmetric Catalysts.

Intermetallic synergy can be useful to both enhance catalytic performance and access diverse chemistries, but understanding and predicting the most effective metal combinations remains a challenge. This perspective focuses on a common class of homogeneous heteronuclear catalysts which combine transition metals (M-(II/III)) with Group III, f-, or s-block metals (M'(I-III)) in phenoxy-imine-ether donor ligands. Independent investigations into these heteronuclear complexes across different fields of catalysis, including electrocatalysis, polymerization catalysis, and small-molecule asymmetric catalysis, have all demonstrated the benefits of intermetallic cooperativity. In both electrocatalysis and polymerization catalysis, similar quantified structure-performance relationships, relating catalytic performance to metal Lewis acidity, have been discovered. This selective perspective article focuses on highlighting the most recent insights and quantified structure-activity relationships in electro- and polymerization catalysis. We then apply the insights and methods, developed separately in these two fields of catalysis, to reanalyze previously reported data for catalytic asymmetric organic transformations. The same quantified structure-performance (i.e., activity or selectivity) trends appear to apply in this third field of homogeneous catalysis. These generally applicable, quantified structure-activity relationships apply to related synergistic heterometallic catalysts across all three disparate fields of chemistry  this finding is both unexpected and very helpful in providing a clearer understanding of how to design catalysts for successful intermetallic synergy. This perspective highlights both the fundamental understanding of such catalytic synergy and the analytical methods used to investigate it. The objective is to provide a guide for both current and future researchers to measure synergistic interactions and to apply those principles to rational catalyst design.