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Highly Strained Arene-Fused 1,2-Diborete Biradicaloid

Gärtner, Annalena, Meier, Lukas, Arrowsmith, Merle, Dietz, Maximilian, Krummenacher, Ivo, Bertermann, Rüdiger, Fantuzzi, Felipe, Braunschweig, Holger (2022) Highly Strained Arene-Fused 1,2-Diborete Biradicaloid. Journal of the American Chemical Society, 144 (46). pp. 21363-21370. ISSN 0002-7863. E-ISSN 1520-5126. (doi:10.1021/jacs.2c09971) (Access to this publication is currently restricted. You may be able to access a copy if URLs are provided) (KAR id:98583)

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The stepwise reduction of a doubly cyclic alkyl(amino)carbene (CAAC)-stabilized 2,3-bis(dibromoboryl)naphthalene enables the isolation of the corresponding mono- and bis(boryl) radicals (one- and two-electron reduction), a 2π-aromatic 1,2-diborete (four-electron reduction), which shows biradical character in the solid-state EPR spectrum, and its cyclic bis(alkylidene)diboron dianion (six-electron reduction). The X-ray crystallographic analysis of the diborete shows a highly strained and twisted four-membered ring with a formal cis-diborene motif featuring a very elongated B–B double bond. Calculations based on DFT and multireference approaches reveal that the diborete possesses an open-shell singlet biradicaloid ground state, which is slightly energetically preferred to its EPR-active triplet-state congener. The addition of CO to the diborete resulted in B–B bond splitting and the formation of the corresponding closed-shell singlet, doubly Lewis base-stabilized bis(borylene), whereas a twofold γ insertion of phenyl azide generates a 1,3-bis(diazenyl)-1,3,2,4-diazadiboretidine.

Item Type: Article
DOI/Identification number: 10.1021/jacs.2c09971
Subjects: Q Science > QD Chemistry
Divisions: Divisions > Division of Natural Sciences > Chemistry and Forensics
Funders: Deutsche Forschungsgemeinschaft (
Depositing User: Felipe Fantuzzi
Date Deposited: 01 Dec 2022 00:38 UTC
Last Modified: 04 Mar 2024 19:57 UTC
Resource URI: (The current URI for this page, for reference purposes)

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