Superseding β-Diketiminato Ligands: An Amido Imidazoline-2-Imine Ligand Stabilizes the Exhaustive Series of B=X Boranes (X=O, S, Se, Te).

Boron reluctantly forms B=X (X=O, S, Se, Te) moieties, which has stimulated the quest for such species in the past few years. Based on the N,N'-chelating β-diketiminato ligand (HNacNac), a new amido imidazoline-2-imine ligand system (HAmIm) is presented, giving rise to the isolation of an exhaustive series of Lewis acid free, monomeric chalcogen B=X boranes with documented π-bond character between boron and the chalcogen. The chalcogenoboranes are isoelectronic and isolobal to the respective ketones. The chemical behavior of the oxoborane (B=O) strongly resembles the classical carbonyl reactivity in C=O bonds. The improved stability provided by HAmIm arises from the formation of more-stable five-membered boron chelates versus the six-membered NacNac analogues and from the imidazoline-2-imine moiety providing enhanced σ- and π-donation. The HAmIm ligand class may supersede the widely employed NacNac system in certain applications.