Two Faces of the Bi−O Bond: Photochemically and Thermally Induced Dehydrocoupling for Si−O Bond Formation

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.