Methylbismuth: an organometallic bismuthinidene biradical
Zitieren Sie bitte immer diese URN: urn:nbn:de:bvb:20-opus-251657
- 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 BiMe\(_3\) 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 experimentallyWe 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 BiMe\(_3\) 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 BiMe\(_3\) to give [BiMe(_2\)]• 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–BiMe\(_2\) bonds could be achieved at moderate temperatures (60–120 °C) in the condensed phase, suggesting that [BiMe\(_2\)]• and BiMe are accessible as reactive intermediates under these conditions.…
Autor(en): | Deb Pratim Mukhopadhyay, Domenik Schleier, Sara Wirsing, Jaqueline Ramler, Dustin Kaiser, Engelbert Reusch, Patrick Hemberger, Tobias Preitschopf, Ivo Krummenacher, Bernd Engels, Ingo Fischer, Crispin Lichtenberg |
---|---|
URN: | urn:nbn:de:bvb:20-opus-251657 |
Dokumentart: | Artikel / Aufsatz in einer Zeitschrift |
Institute der Universität: | Fakultät für Chemie und Pharmazie / Institut für Anorganische Chemie |
Fakultät für Chemie und Pharmazie / Institut für Physikalische und Theoretische Chemie | |
Sprache der Veröffentlichung: | Englisch |
Titel des übergeordneten Werkes / der Zeitschrift (Englisch): | Chemical Science |
Erscheinungsjahr: | 2020 |
Band / Jahrgang: | 11 |
Heft / Ausgabe: | 29 |
Seitenangabe: | 7562-7568 |
Originalveröffentlichung / Quelle: | Chemical Science (2020), 11:33, 7562-7568. https://doi.org/10.1039/D0SC02410D |
URL der Erstveröffentlichung: | https://pubs.rsc.org/en/content/articlelanding/2020/SC/D0SC02410D |
DOI: | https://doi.org/10.1039/D0SC02410D |
Sonstige beteiligte Institutionen: | Paul Scherrer Institut |
Allgemeine fachliche Zuordnung (DDC-Klassifikation): | 5 Naturwissenschaften und Mathematik / 54 Chemie / 546 Anorganische Chemie |
Normierte Schlagworte (GND): | Photoelektronenspektroskopie |
Freie Schlagwort(e): | methylbismuth |
Datum der Freischaltung: | 20.12.2021 |
Lizenz (Deutsch): | CC BY-NC: Creative-Commons-Lizenz: Namensnennung, Nicht kommerziell |