Structural Snapshots on Stepwise Anionic Oxoborane Formation: Access to an Acyclic BO Ketone Analogue and Its Metathesis Chemistry with CO<sub>2</sub> and CS<sub>2</sub>
In this work, we disclose the synthesis and characterization of non-acid/base-stabilized anionic oxoboranes [<sup>Mes</sup>Ter<sub>2</sub>BO][K(L)] (<sup>Mes</sup>Ter = -C<sub>6</sub>H<sub>3</sub>-2,6-(2,4,6-Me<sub>3</sub>-C<sub>6</sub>H<sub>2</sub>)<sub>2</sub>, L = [2.2.2]-cryptand or 18-crown-6), which are isoelectronic and isostructural with aryl-substituted ketones. The stepwise synthetic formation of these ion-separated oxoboranes is demonstrated on the one hand by the treatment of the parent borinic acid <sup>Mes</sup>Ter<sub>2</sub>BOH with <i>N</i>-heterocyclic carbenes (NHCs) to give [<sup>Mes</sup>Ter<sub>2</sub>BO][HNHC] derivatives, and on the other hand by a deprotonation-sequestration sequence. Bearing polarized boron-oxygen moieties, their inherent reactivity toward both carbon disulfide and carbon dioxide reveals a unique π-bond metathesis reactivity to yield [(<sup>Mes</sup>Ter)<sub>2</sub>B-μ-E<sub>2</sub>C=E][K(L)] (E = O, S) derivatives.
Authors
- Daniel Duvinage (ORCID: https://orcid.org/0000-0002-9387-7172)
- Jens Beckmann (ORCID: https://orcid.org/0000-0002-8548-1821)
- Malte Fischer (ORCID: https://orcid.org/0000-0002-2806-1302)
- Christopher Golz (ORCID: https://orcid.org/0009-0001-8865-3254)
- Emanuel Hupf (ORCID: https://orcid.org/0000-0003-0121-7554)
- Michael Heitmann
Institutions
- University of Bremen (DE)
- University of Göttingen (DE)
Publication Details
- Journal
- Inorganic Chemistry
- Published
- 2025-02-05
- DOI
- https://doi.org/10.1021/acs.inorgchem.4c05354
- Citations
- 4
- Primary Topic
- Organoboron and organosilicon chemistry
- Type
- article
- Field-Weighted Citation Impact
- 3.74
Funders
- Verband der Chemischen Industrie
- Deutsche Forschungsgemeinschaft
- Georg-August-Universität Göttingen