Structural Snapshots on Stepwise Anionic Oxoborane Formation: Access to an Acyclic BO Ketone Analogue and Its Metathesis Chemistry with CO2 and CS2.

Heitmann M., Duvinage D., Golz C., Hupf E., Beckmann J., Fischer M.

In this work, we disclose the synthesis and characterization of non-acid/base-stabilized anionic oxoboranes [MesTer2BO][K(L)] (MesTer = -C6H3-2,6-(2,4,6-Me3-C6H2)2, 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 MesTer2BOH with N-heterocyclic carbenes (NHCs) to give [MesTer2BO][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 [(MesTer)2B-μ-E2C=E][K(L)] (E = O, S) derivatives.

DOI

10.1021/acs.inorgchem.4c05354

Type

Journal article

Publication Date

2025-02-17T00:00:00+00:00

Volume

64

Pages

3028 - 3037

Total pages

9

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