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Two Faces of the Bi−O Bond: Photochemically and Thermally Induced Dehydrocoupling for Si−O Bond Formation
Please always quote using this URN: urn:nbn:de:bvb:20-opus-257428
- 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.…
Author: | Jacqueline Ramler, Johannes Schwarzmann, Andreas Stoy, Crispin LichtenbergORCiD |
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URN: | urn:nbn:de:bvb:20-opus-257428 |
Document Type: | Journal article |
Faculties: | Fakultät für Chemie und Pharmazie / Institut für Anorganische Chemie |
Language: | English |
Parent Title (English): | European Journal of Inorganic Chemistry |
Year of Completion: | 2022 |
Volume: | 2022 |
Issue: | 7 |
Article Number: | e202100934 |
Source: | European Journal of Inorganic Chemistry 2022, Volume 2022(7):e202100934. DOI: 10.1002/ejic.202100934 |
DOI: | https://doi.org/10.1002/ejic.202100934 |
Dewey Decimal Classification: | 5 Naturwissenschaften und Mathematik / 54 Chemie / 546 Anorganische Chemie |
Tag: | Bismuth; catalysis; chalcogens; dehydrocoupling; radical reactions |
Release Date: | 2022/03/22 |
EU-Project number / Contract (GA) number: | 946184 |
OpenAIRE: | OpenAIRE |
Licence (German): | CC BY-NC-ND: Creative-Commons-Lizenz: Namensnennung, Nicht kommerziell, Keine Bearbeitungen 4.0 International |