Isolation of neutral, mono-, and dicationic B\(_2\)P\(_2\) rings by diphosphorus addition to a boron-boron triple bond

Please always quote using this URN: urn:nbn:de:bvb:20-opus-256451
  • The NHC-stabilised diboryne (B\(_2\)(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 B\(_2\)P\(_2\) 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 toThe NHC-stabilised diboryne (B\(_2\)(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 B\(_2\)P\(_2\) 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 B\(_2\)P\(_2\) rings, with their diradicaloid, planar-ring isomers lying close in energy.show moreshow less

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Metadaten
Author: Tobias Brückner, Felipe FantuzziORCiD, Tom E. Stennett, Ivo KrummenacherORCiD, Rian D. DewhurstORCiD, Bernd EngelsORCiD, Holger BraunschweigORCiD
URN:urn:nbn:de:bvb:20-opus-256451
Document Type:Journal article
Faculties:Fakultät für Chemie und Pharmazie / Institut für Anorganische Chemie
Fakultät für Chemie und Pharmazie / Institut für Physikalische und Theoretische Chemie
Language:English
Parent Title (English):Angewandte Chemie International Edition
Year of Completion:2021
Volume:60
Issue:24
Pagenumber:13661–13665
Source:Angewandte Chemie International Edition (2021) 60:24, 13661–13665. DOI: 10.1002/anie.202102218
DOI:https://doi.org/10.1002/anie.202102218
Dewey Decimal Classification:5 Naturwissenschaften und Mathematik / 54 Chemie / 546 Anorganische Chemie
Tag:boron; density functional calculations; inorganic chemistry; oxidation; phosphorus heterocycles; radicals
Release Date:2022/02/24
EU-Project number / Contract (GA) number:669054
OpenAIRE:OpenAIRE
Licence (German):License LogoCC BY: Creative-Commons-Lizenz: Namensnennung 4.0 International