Main group bimetallic partnerships for cooperative catalysis

Over the past decade s-block metal catalysis has undergone a transformation from being an esoteric curiosity to a well-established and consolidated field towards sustainable synthesis. Earth-abundant metals such as Ca, Mg, and Al have shown eye-opening catalytic performances in key catalytic processes such as hydrosilylation, hydroamination or alkene polymerization. In parallel to these studies, s-block mixed-metal reagents have also been attracting widespread interest from scientists. These bimetallic reagents effect many cornerstone organic transformations, often providing enhanced reactivities and better chemo- and regioselectivities than conventional monometallic reagents. Despite a significant number of synthetic advances to date, most efforts have focused primarily on stoichiometric transformations. Merging these two exciting areas of research, this Perspective Article provides an overview on the emerging concept of s/p-block cooperative catalysis. Showcasing recent contributions from several research groups across the world, the untapped potential that these systems can offer in catalytic transformations is discussed with special emphasis placed on how synergistic effects can operate and the special roles played by each metal in these transformations. Advancing the understanding of the ground rules of s-block cooperative catalysis, the application of these bimetalic systems in a critical selection of catalytic transformations encompassing hydroamination, cyclisation, hydroboration to C-C bond forming processes are presented as well as their uses in important polymerization reactions. Exporting cooperative effects in main group heterobimetallic reagents to catalytic regimes, this Perspective showcases key advances in their applications for hydroelementation, cyclisation, C-C bond formation and polymerization processes.