Two Faces of the Bi-O Bond: Photochemically and Thermally Induced Dehydrocoupling for Si-O Bond Formation.
Jacqueline RamlerJohannes SchwarzmannAndreas StoyCrispin LichtenbergPublished in: European journal of inorganic chemistry (2021)
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.
Keyphrases
- density functional theory
- high resolution
- solid state
- mass spectrometry
- molecular dynamics
- electron transfer
- crystal structure
- liquid chromatography
- single molecule
- molecular dynamics simulations
- molecular docking
- room temperature
- transition metal
- diabetic rats
- drug induced
- magnetic resonance imaging
- electron microscopy
- high performance liquid chromatography
- aqueous solution
- oxide nanoparticles
- high speed
- atomic force microscopy
- ms ms
- ionic liquid
- dual energy