Photochemical and Thermal Activation of a Diarylbismuth Azide
- 1Institute of Inorganic Chemistry University of Bonn Bonn Germany
- 2Clausius‐Institut für Physikalische und Theoretische Chemie University of Bonn Bonn Germany
Abstract
Azides are widely employed in synthesis as convenient nitrene precursors, particularly in transition‐metal chemistry, where metal–nitrene intermediates enable diverse C─H amination, aziridination, and atom‐transfer processes. In stark contrast, main‐group azides, especially bismuth ones, are underrepresented and have not been fully exploited as nitrene sources. Herein, we report the synthesis and full characterization of a diarylbismuth monoazide supported by a diphenylsulfone‐based dianionic ligand. The complex is robust toward air, moisture, and elevated temperatures, enabling detailed photochemical and chemical studies. Ultrafast UV‐pump/mid‐IR‐probe spectroscopy demonstrates that 266 nm excitation triggers rapid azide‐to‐ligand charge transfer and loss of the azide antisymmetric stretching band. FTIR‐monitored trapping with t‐butyl isonitrile produces a new absorption band in the heterocumulene region, suggesting the formation of a nitrene intermediate. Alternatively, Lewis‐acid activation with B(C6F5)3 produces a stable adduct that undergoes thermal N2 extrusion, transmetalation, and cycloaddition to form a tetrazaborole dimer. These divergent activation pathways establish bismuth azides as viable nitrene precursors and expand the reactivity landscape of heavy p‐block chemistry.
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BibTeX
@article{pugliese2026photochemical,
title = {{Photochemical and Thermal Activation of a Diarylbismuth Azide}},
author = {Giacomo Pugliese and Oliver Pichl and Gregor Schnakenburg and Peter Vöhringer and Luis I. Domenianni and Alessandro Bismuto},
journal = {Chemistry (Weinheim an Der Bergstrasse, Germany)},
year = {2026},
month = aug,
doi = {10.1002/chem.71556},
url = {https://doi.org/10.1002/chem.71556},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Photochemical and Thermal Activation of a Diarylbismuth Azide
AU - Giacomo Pugliese
AU - Oliver Pichl
AU - Gregor Schnakenburg
AU - Peter Vöhringer
AU - Luis I. Domenianni
AU - Alessandro Bismuto
PY - 2026
DA - 2026/08/13
JO - Chemistry (Weinheim an Der Bergstrasse, Germany)
DO - 10.1002/chem.71556
UR - https://doi.org/10.1002/chem.71556
AB - Azides are widely employed in synthesis as convenient nitrene precursors, particularly in transition‐metal chemistry, where metal–nitrene intermediates enable diverse C─H amination, aziridination, and atom‐transfer processes. In stark contrast, main‐group azides, especially bismuth ones, are underrepresented and have not been fully exploited as nitrene sources. Herein, we report the synthesis and full characterization of a diarylbismuth monoazide supported by a diphenylsulfone‐based dianionic ligand. The complex is robust toward air, moisture, and elevated temperatures, enabling detailed photochemical and chemical studies. Ultrafast UV‐pump/mid‐IR‐probe spectroscopy demonstrates that 266 nm excitation triggers rapid azide‐to‐ligand charge transfer and loss of the azide antisymmetric stretching band. FTIR‐monitored trapping with t‐butyl isonitrile produces a new absorption band in the heterocumulene region, suggesting the formation of a nitrene intermediate. Alternatively, Lewis‐acid activation with B(C6F5)3 produces a stable adduct that undergoes thermal N2 extrusion, transmetalation, and cycloaddition to form a tetrazaborole dimer. These divergent activation pathways establish bismuth azides as viable nitrene precursors and expand the reactivity landscape of heavy p‐block chemistry.
SN - 0947-6539
SN - 1521-3765
ER -