Journal article
Methylbismuth: an organometallic bismuthinidene biradical.
- Mukhopadhyay DP Institute of Physical and Theoretical Chemistry , University of Würzburg , Am Hubland , D-97074 Würzburg , Germany . Email: bernd.engels@uni-wuerzburg.de ; Email: ingo.fischer@uni-wuerzburg.de.
- Schleier D Institute of Physical and Theoretical Chemistry , University of Würzburg , Am Hubland , D-97074 Würzburg , Germany . Email: bernd.engels@uni-wuerzburg.de ; Email: ingo.fischer@uni-wuerzburg.de.
- Wirsing S Institute of Physical and Theoretical Chemistry , University of Würzburg , Am Hubland , D-97074 Würzburg , Germany . Email: bernd.engels@uni-wuerzburg.de ; Email: ingo.fischer@uni-wuerzburg.de.
- Ramler J Institute of Inorganic Chemistry , University of Würzburg , Am Hubland , D-97074 Würzburg , Germany . Email: crispin.lichtenberg@uni-wuerzburg.de.
- Kaiser D Institute of Physical and Theoretical Chemistry , University of Würzburg , Am Hubland , D-97074 Würzburg , Germany . Email: bernd.engels@uni-wuerzburg.de ; Email: ingo.fischer@uni-wuerzburg.de.
- Reusch E Institute of Physical and Theoretical Chemistry , University of Würzburg , Am Hubland , D-97074 Würzburg , Germany . Email: bernd.engels@uni-wuerzburg.de ; Email: ingo.fischer@uni-wuerzburg.de.
- Hemberger P Laboratory for Femtochemistry and Synchrotron Radiation , Paul Scherrer Institut (PSI) , CH-5232 Villigen , Switzerland . Email: patrick.hemberger@psi.ch.
- Preitschopf T Institute of Physical and Theoretical Chemistry , University of Würzburg , Am Hubland , D-97074 Würzburg , Germany . Email: bernd.engels@uni-wuerzburg.de ; Email: ingo.fischer@uni-wuerzburg.de.
- Krummenacher I Institute of Inorganic Chemistry , University of Würzburg , Am Hubland , D-97074 Würzburg , Germany . Email: crispin.lichtenberg@uni-wuerzburg.de.
- Engels B Institute of Physical and Theoretical Chemistry , University of Würzburg , Am Hubland , D-97074 Würzburg , Germany . Email: bernd.engels@uni-wuerzburg.de ; Email: ingo.fischer@uni-wuerzburg.de.
- Fischer I Institute of Physical and Theoretical Chemistry , University of Würzburg , Am Hubland , D-97074 Würzburg , Germany . Email: bernd.engels@uni-wuerzburg.de ; Email: ingo.fischer@uni-wuerzburg.de.
- Lichtenberg C Institute of Inorganic Chemistry , University of Würzburg , Am Hubland , D-97074 Würzburg , Germany . Email: crispin.lichtenberg@uni-wuerzburg.de.
- 2020-09-03
Published in:
- Chemical science. - 2020
English
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.
- Language
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- English
- Open access status
- gold
- Identifiers
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- DOI 10.1039/d0sc02410d
- PMID 32874526
- Persistent URL
- https://folia.unifr.ch/global/documents/25389
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