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Two Faces of the Bi−O Bond: Photochemically and Thermally Induced Dehydrocoupling for Si−O Bond Formation
Author(s) -
Ramler Jacqueline,
Schwarzmann Johannes,
Stoy Andreas,
Lichtenberg Crispin
Publication year - 2022
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.202100934
Subject(s) - chemistry , homolysis , heterolysis , bond cleavage , photochemistry , electron paramagnetic resonance , stoichiometry , silanes , phenol , catalysis , spectroscopy , nuclear magnetic resonance spectroscopy , single crystal , silylation , radical , crystallography , organic chemistry , nuclear magnetic resonance , physics , silane , quantum mechanics
Abstract 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 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.