Frontiers in the Solution-Phase Chemistry of Homoatomic Group 15 Zintl Clusters

Although discovered more than a century ago, the study of Zintl anions is experiencing a renaissance. Initial investigations on Zintl anions were focused on the structure, bonding, and physical properties of both the solid-state Zintl phases and solution-state solvated salts. Advances over the last few decades included their reactivity with transition metals where both exo-coordination and encapsulation have been observed, organic derivatization, their oligomerisation chemistry, and the preparation of heteroatomic systems. Reports on these developments have been previously discussed and reviewed. Herein, we present the most recent developments in the solution-state chemistry of homoatomic group 15 Zintl clusters and an outlook for the field. We believe frontiers in this area are best represented by recent additions to the library of homoatomic polybismuthide clusters, new synthetic routes for the preparation and functionlisation of homoatomic group 15 clusters, and small molecule activation using group 15 homoatomic Zintl clusters.