Radical Activation of N-H and O-H Bonds 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 complex based on bismuth featuring an extremely weak Bi-O bond, which permits the in situ generation of reactive Bi(II) species. The ensuing organobismuth(II) engages with various amines and alcohols and exerts an unprecedented effect onto the X-H bond, 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-center dot sources, thus providing alternative pathways for main group chemistry.

Automated summary

The development of unconventional strategies for the activation of ammonia and water is crucial for sustainable chemistry. In this study, a radical equilibrium complex based on bismuth is synthesized and characterized, which allows for the in situ generation of reactive Bi(II) species. The resulting organobismuth(II) complex exhibits unprecedented effects on various X-H bonds and enables rapid radical activation of N-H and O-H bonds, leading to the formation of Bi(III)-amido and -alkoxy complexes. Furthermore, the Bi(III)-N complexes show unique reactivity towards H+, H-, and H· sources, providing alternative pathways for main group chemistry.