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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.…
Author: | Tobias Brückner, Felipe FantuzziORCiD, Tom E. Stennett, Ivo KrummenacherORCiD, Rian D. DewhurstORCiD, Bernd EngelsORCiD, Holger BraunschweigORCiD |
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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): | CC BY: Creative-Commons-Lizenz: Namensnennung 4.0 International |