Diaryl Bismuthides and Acyl Bismuthanes Enable Visible-Light-Induced Reversible Carbon Monoxide Insertion and Extrusion

Felix Geist, Benedikt Narz, Darian Boguslawski, Tobias Dunaj, Sascha Reith, Jordi Poater and Crispin Lichtenberg ()
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Felix Geist: Department of Chemistry Philipps-Universität Marburg, Hans-Meerwein-Str. 4
Benedikt Narz: Department of Chemistry Philipps-Universität Marburg, Hans-Meerwein-Str. 4
Darian Boguslawski: Department of Chemistry Philipps-Universität Marburg, Hans-Meerwein-Str. 4
Tobias Dunaj: Department of Chemistry Philipps-Universität Marburg, Hans-Meerwein-Str. 4
Sascha Reith: Department of Chemistry Philipps-Universität Marburg, Hans-Meerwein-Str. 4
Jordi Poater: Departament de Química Inorgànica i Orgànica & IQTCUB, Universitat de Barcelona
Crispin Lichtenberg: Department of Chemistry Philipps-Universität Marburg, Hans-Meerwein-Str. 4

Nature Communications, 2025, vol. 16, issue 1, 1-7

Abstract: Abstract Carbon monoxide (CO) is one of the simplest and most fundamental molecules that has fascinated chemists for decades. Early-on, chemists have recognized and exploited its favorable properties as a key reagent in large-scale metallurgical processes, productions of base- and fine chemicals, and (more recently) potential medical applications. Most of these transformations rely on reactions that proceed in the coordination sphere of transition metals, with reversible reactions playing a crucial role in catalytic transformations. Recent endeavors have brought main group elements on the stage of carbonyl chemistry (carbonyl = metal-bound CO), but reversible reactions (especially insertion and extrusion reactions) are very rare and remain limited to examples of thermal initiation. Here we show that an innovative access to acyl-bismuth compounds, R2Bi–C(O)R’, can be granted in a stepwise redox approach. The target compounds could be isolated and fully characterized. As a unique feature, these complexes enable the visible-light-driven reversible CO extrusion and insertion of carbon monoxide in the coordination sphere of a main group metal.

Date: 2025
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DOI: 10.1038/s41467-025-66412-5

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