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August 15, 2026Chemistry - A European JournalOpen Access

Photochemical and Thermal Activation of a Diarylbismuth Azide

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Authors

GPGiacomo PuglieseOspedale MaggioreOPOliver PichlSchiller International UniversityGSGregor SchnakenburgUniversity of Bonn

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Overview

Spectroscopic and chemical analysis reveals photochemical and thermal activation pathways for diarylbismuth azide, indicating bismuth complexes can serve as viable nitrene precursors.

Key Points

  • Synthesize a stable diarylbismuth monoazide and evaluate its viability as a main-group nitrene precursor through photochemical and thermal activation.
  • Synthesized and characterized a diarylbismuth monoazide supported by a diphenylsulfone-based dianionic ligand.
  • Tracked photoexcitation using ultrafast UV-pump/mid-IR-probe spectroscopy at 266 nm alongside FTIR-monitored trapping with t-butyl isonitrile.
  • Tested Lewis-acid activation using B(C6F5)3 to probe thermal dinitrogen extrusion and downstream reactivity.
  • Ultrafast 266 nm photoexcitation induced rapid azide-to-ligand charge transfer and loss of the azide antisymmetric stretching band, with isonitrile trapping signaling nitrene intermediate formation.
  • Lewis-acid activation with B(C6F5)3 generated a stable adduct that underwent thermal N2 extrusion, transmetalation, and cycloaddition to yield a tetrazaborole dimer.

Cite This Study

Pugliese et al. (2026) studied this question.

synapsesocial.com/papers/6a801a1a75c2e31742c869bbhttps://doi.org/10.1002/chem.71556
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