Isolation of Neutral, Mono-, and Dicationic B
| العنوان: | Isolation of Neutral, Mono-, and Dicationic B |
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| المؤلفون: | Tobias, Brückner, Felipe, Fantuzzi, Tom E, Stennett, Ivo, Krummenacher, Rian D, Dewhurst, Bernd, Engels, Holger, Braunschweig |
| المصدر: | Angewandte Chemie (International Ed. in English) |
| سنة النشر: | 2021 |
| مصطلحات موضوعية: | oxidation, Communication, density functional calculations, Heterocycles, boron, radicals, Communications, phosphorus heterocycles |
| الوصف: | 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. Room temperature P−P bond addition to an NHC‐stabilised diboryne yielded a four‐membered B2P2 heterocycle, which can be further oxidised to a radical cation and a dication depending on the oxidation reagent and its counterion. |
| تدمد: | 1521-3773 |
| URL الوصول: | https://explore.openaire.eu/search/publication?articleId=pmid________::a39770fcbcdd2de028b6b25c40b97f28 https://pubmed.ncbi.nlm.nih.gov/33844394 |
| حقوق: | OPEN |
| رقم الأكسشن: | edsair.pmid..........a39770fcbcdd2de028b6b25c40b97f28 |
| قاعدة البيانات: | OpenAIRE |
| تدمد: | 15213773 |
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