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Isolation of Neutral, Mono-, and Dicationic B2P2 Rings by Diphosphorus Addition to a Boron−Boron Triple Bond

Brückner, Tobias, Fantuzzi, Felipe, Stennett, Tom E., Krummenacher, Ivo, Dewhurst, Rian D., Engels, Bernd, Braunschweig, Holger (2021) Isolation of Neutral, Mono-, and Dicationic B2P2 Rings by Diphosphorus Addition to a Boron−Boron Triple Bond. Angewandte Chemie International Edition, 60 (24). pp. 13661-13665. ISSN 1433-7851. E-ISSN 1521-3773. (doi:10.1002/anie.202102218) (KAR id:96286)

Abstract

The NHC-stabilised diboryne (B2(SIDep)2; SIDep=1,3-bis(2,6-diethylphenyl)imidazolin-2-ylidene) undergoes a high-yielding P−P bond activation with tetraethyldiphosphine at room temperature to form a B2P2 heterocycle via a diphosphoryldiborene by 1,2-diphosphination. The heterocycle can be oxidised to a radical cation and a dication, respectively, depending on the oxidant used and its counterion. Starting from the planar, neutral 1,3-bis(alkylidene)-1,3-diborata-2,4-diphosphoniocyclobutane, each oxidation step leads to decreased B−B distances and loss of planarity by cationisation. X-ray analyses in conjunction with DFT and CASSCF/NEVPT2 calculations reveal closed-shell singlet, butterfly-shaped structures for the NHC-stabilised dicationic B2P2 rings, with their diradicaloid, planar-ring isomers lying close in energy.

Item Type: Article
DOI/Identification number: 10.1002/anie.202102218
Subjects: Q Science > QD Chemistry
Divisions: Divisions > Division of Natural Sciences > Chemistry and Forensics
Depositing User: Felipe Fantuzzi
Date Deposited: 18 Aug 2022 08:40 UTC
Last Modified: 19 Aug 2022 08:59 UTC
Resource URI: https://kar.kent.ac.uk/id/eprint/96286 (The current URI for this page, for reference purposes)

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