Two Faces of the Bi−O Bond: Photochemically and Thermally Induced Dehydrocoupling for Si−O Bond Formation
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- The diorgano(bismuth)alcoholate [Bi((C\(_{6}\)H\(_{4}\)CH\(_{2}\))\(_{2}\)S)OPh] (1-OPh) has been synthesized and fully characterized. Stoichiometric reactions, UV/Vis spectroscopy, and (TD-)DFT calculations suggest its susceptibility to homolytic and heterolytic Bi−O bond cleavage under given reaction conditions. Using the dehydrocoupling of silanes with either TEMPO or phenol as model reactions, the catalytic competency of 1-OPh has been investigated (TEMPO=(tetramethyl-piperidin-1-yl)-oxyl). Different reaction pathways can deliberately beThe diorgano(bismuth)alcoholate [Bi((C\(_{6}\)H\(_{4}\)CH\(_{2}\))\(_{2}\)S)OPh] (1-OPh) has been synthesized and fully characterized. Stoichiometric reactions, UV/Vis spectroscopy, and (TD-)DFT calculations suggest its susceptibility to homolytic and heterolytic Bi−O bond cleavage under given reaction conditions. Using the dehydrocoupling of silanes with either TEMPO or phenol as model reactions, the catalytic competency of 1-OPh has been investigated (TEMPO=(tetramethyl-piperidin-1-yl)-oxyl). Different reaction pathways can deliberately be addressed by applying photochemical or thermal reaction conditions and by choosing radical or closed-shell substrates (TEMPO vs. phenol). Applied analytical techniques include NMR, UV/Vis, and EPR spectroscopy, mass spectrometry, single-crystal X-ray diffraction analysis, and (TD)-DFT calculations.…
Autor(en): | Jacqueline Ramler, Johannes Schwarzmann, Andreas Stoy, Crispin LichtenbergORCiD |
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URN: | urn:nbn:de:bvb:20-opus-257428 |
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): | European Journal of Inorganic Chemistry |
Erscheinungsjahr: | 2022 |
Band / Jahrgang: | 2022 |
Heft / Ausgabe: | 7 |
Aufsatznummer: | e202100934 |
Originalveröffentlichung / Quelle: | European Journal of Inorganic Chemistry 2022, Volume 2022(7):e202100934. DOI: 10.1002/ejic.202100934 |
DOI: | https://doi.org/10.1002/ejic.202100934 |
Allgemeine fachliche Zuordnung (DDC-Klassifikation): | 5 Naturwissenschaften und Mathematik / 54 Chemie / 546 Anorganische Chemie |
Freie Schlagwort(e): | Bismuth; catalysis; chalcogens; dehydrocoupling; radical reactions |
Datum der Freischaltung: | 22.03.2022 |
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 |