Issue 29, 2020

Methylbismuth: an organometallic bismuthinidene biradical

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.

Graphical abstract: Methylbismuth: an organometallic bismuthinidene biradical

Supplementary files

Article information

Article type
Edge Article
Submitted
28 Apr 2020
Accepted
02 Jun 2020
First published
03 Jun 2020
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2020,11, 7562-7568

Methylbismuth: an organometallic bismuthinidene biradical

D. P. Mukhopadhyay, D. Schleier, S. Wirsing, J. Ramler, D. Kaiser, E. Reusch, P. Hemberger, T. Preitschopf, I. Krummenacher, B. Engels, I. Fischer and C. Lichtenberg, Chem. Sci., 2020, 11, 7562 DOI: 10.1039/D0SC02410D

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