02.08.2026 First Anionic & Homoleptic Bismuth Amide!

Vary the charge: neutral and cationic bismuth amides have been established as important building blocks in synthetic chemistry, catalysts, and sources of monodisperse nanoparticles in recent years. Here we report for the first time a homoleptic anionic bismuth(III) amide, [Bi(NR₂)₄]^–. Bonding analyses reveal two distinguishable groups of (NR₂)^– ligands in a bisphenoidal coordination geometry that are rapidly interconverted via a Berry pseudorotation. The anionic complex is accompanied by its neutral and its cationic congener, completing the first series of charged bismuth amides with insights into the effect of charge on bonding and reactivity. This work has just been accepted for publication in Chem. Commun. and will be incorporated in the Pioneering Investigators series. Congratulations to all the contributors!