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Updated: Dec 10, 2025

Imine Metathesis by Silica-Supported Catalysts Using the Methodology of Surface Organometallic Chemistry
Published on: October 18, 2019
Methylbismuth: an organometallic bismuthinidene biradical
Deb Pratim Mukhopadhyay1, Domenik Schleier1, Sara Wirsing1
1Institute of Physical and Theoretical Chemistry , University of Würzburg , Am Hubland , D-97074 Würzburg , Germany . Email: bernd.engels@uni-wuerzburg.de ;
Abstract:
We report the generation, spectroscopic characterization, and computational analysis of the first free (non-stabilized) organometallic bismuthinidene, BiMe. The title compound was generated in situ from BiMe3 by controlled homolytic Bi-C bond cleavage in the gas phase. Its electronic structure was characterized by a combination of photoion mass-selected threshold photoelectron spectroscopy and DFT as well as multi-reference computations. A triplet ground state was identified and an ionization energy (IE) of 7.88 eV was experimentally determined. Methyl abstraction from BiMe3 to give [BiMe2]• is a key step in the generation of BiMe. We reaveal a bond dissociation energy of 210 ± 7 kJ mol-1, which is substantially higher than the previously accepted value. Nevertheless, the homolytic cleavage of Me-BiMe2 bonds could be achieved at moderate temperatures (60-120 °C) in the condensed phase, suggesting that [BiMe2]• and BiMe are accessible as reactive intermediates under these conditions.
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