Radical Activation of Ammonia and Water at Bismuth(II)

The development of unconventional strategies for the activation of ammonia (NH3) and water (H2O) is of capital importance for the advancement of sustainable chemical strategies. Herein we provide the synthesis and characterization of a Radical Equilibrium Com-plex based on bismuth featuring an extremely weak Bi‒O bond, that permits the in situ generation of reactive Bi(II) species. The en-suing organobismuth(II) engages with various ammines and alcohols and exerts an unprecedented effect onto the X‒H, leading to low BDFEX-H. As a result, radical activation of various N‒H and O‒H bonds—including ammonia and water—occurs in seconds at room temperature, delivering well-defined Bi(III)-amido and -alkoxy complexes. Moreover, we demonstrate that the resulting Bi(III)‒N complexes engage in a unique reactivity pattern with the triad of H+, H‒ and H· sources, thus providing alternative pathways for main group chemistry.