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Radical Activation of N–H and O–H Bonds at Bismuth(II)

[Image: see text] The development of unconventional strategies for the activation of ammonia (NH(3)) and water (H(2)O) 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 bismu...

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Detalles Bibliográficos
Autores principales: Yang, Xiuxiu, Reijerse, Edward J., Bhattacharyya, Kalishankar, Leutzsch, Markus, Kochius, Markus, Nöthling, Nils, Busch, Julia, Schnegg, Alexander, Auer, Alexander A., Cornella, Josep
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2022
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9479083/
https://www.ncbi.nlm.nih.gov/pubmed/36053726
http://dx.doi.org/10.1021/jacs.2c05882
Descripción
Sumario:[Image: see text] The development of unconventional strategies for the activation of ammonia (NH(3)) and water (H(2)O) 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 BDFE(X–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.