Bismuth Amides Mediate Facile and Highly Selective Pn–Pn Radical‐Coupling Reactions (Pn=N, P, As)
Zitieren Sie bitte immer diese URN: urn:nbn:de:bvb:20-opus-236582
- The controlled release of well‐defined radical species under mild conditions for subsequent use in selective reactions is an important and challenging task in synthetic chemistry. We show here that simple bismuth amide species [Bi(NAr\(_2\))\(_3\)] readily release aminyl radicals [NAr\(_2\)]. at ambient temperature in solution. These reactions yield the corresponding hydrazines, Ar\(_2\)N−NAr\(_2\), as a result of highly selective N−N coupling. The exploitation of facile homolytic Bi−Pn bond cleavage for Pn−Pn bond formation was extended toThe controlled release of well‐defined radical species under mild conditions for subsequent use in selective reactions is an important and challenging task in synthetic chemistry. We show here that simple bismuth amide species [Bi(NAr\(_2\))\(_3\)] readily release aminyl radicals [NAr\(_2\)]. at ambient temperature in solution. These reactions yield the corresponding hydrazines, Ar\(_2\)N−NAr\(_2\), as a result of highly selective N−N coupling. The exploitation of facile homolytic Bi−Pn bond cleavage for Pn−Pn bond formation was extended to higher homologues of the pnictogens (Pn=N–As): homoleptic bismuth amides mediate the highly selective dehydrocoupling of HPnR\(_2\) to give R\(_2\)Pn−PnR\(_2\). Analyses by NMR and EPR spectroscopy, single‐crystal X‐ray diffraction, and DFT calculations reveal low Bi−N homolytic bond‐dissociation energies, suggest radical coupling in the coordination sphere of bismuth, and reveal electronic and steric parameters as effective tools to control these reactions.…
Autor(en): | Kai Oberdorf, Anna Hanft, Jacqueline Ramler, Ivo Krummenacher, Matthias Bickelhaupt, Jordi Poater, Crispin Lichtenberg |
---|---|
URN: | urn:nbn:de:bvb:20-opus-236582 |
Dokumentart: | Artikel / Aufsatz in einer Zeitschrift |
Institute der Universität: | Fakultät für Chemie und Pharmazie / Institut für Anorganische Chemie |
Sprache der Veröffentlichung: | Englisch |
Titel des übergeordneten Werkes / der Zeitschrift (Englisch): | Angewandte Chemie, International Edition |
Erscheinungsjahr: | 2021 |
Band / Jahrgang: | 60 |
Heft / Ausgabe: | 12 |
Seitenangabe: | 6441-6445 |
Originalveröffentlichung / Quelle: | Angewandte Chemie, International Edition 2021,60, 6441–6445. https://doi.org/10.1002/anie.202015514 |
DOI: | https://doi.org/10.1002/anie.202015514 |
Allgemeine fachliche Zuordnung (DDC-Klassifikation): | 5 Naturwissenschaften und Mathematik / 54 Chemie / 546 Anorganische Chemie |
Freie Schlagwort(e): | aminyl radicals; bismuth amides; diphosphanes; heavier pnictogens; pnictogen coupling; radical coupling; radical species |
Datum der Freischaltung: | 03.05.2021 |
EU-Projektnummer / Contract (GA) number: | 946184 |
OpenAIRE: | OpenAIRE |
Lizenz (Deutsch): | CC BY-NC-ND: Creative-Commons-Lizenz: Namensnennung, Nicht kommerziell, Keine Bearbeitungen 4.0 International |