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Titel:Two Faces of the Bi O Bond: Photochemically and Thermally Induced Dehydrocoupling for Si O Bond Formation
Autor:Jacqueline Ramler
Weitere Verfasser:Johannes Schwarzmann; Andreas Stoy; Crispin Lichtenberg
Veröffentlicht:2022
URI:https://archiv.ub.uni-marburg.de/es/2022/0015
DOI: https://doi.org/10.17192/es2022.0015
URN: urn:nbn:de:hebis:04-es2022-00155
DDC:540 Chemie
Publikationsdatum:2022-03-14
Lizenz:https://creativecommons.org/licenses/by-nc-nd/4.0/

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Summary:
The diorgano(bismuth)alcoholate [Bi((C6H4CH2)2S)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.


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