TY  - JOUR
A1  - Ramler, Jacqueline
A1  - Schwarzmann, Johannes
A1  - Stoy, Andreas
A1  - Lichtenberg, Crispin
T1  - Two Faces of the Bi−O Bond: Photochemically and Thermally Induced Dehydrocoupling for Si−O Bond Formation
JF  - European Journal of Inorganic Chemistry
N2  - 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.
KW  - Bismuth
KW  - dehydrocoupling
KW  - radical reactions
KW  - chalcogens
KW  - catalysis
Y1  - 2022
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-257428
VL  - 2022
IS  - 7
ER  - 
TY  - JOUR
A1  - Ramler, Jacqueline
A1  - Krummenacher, Ivo
A1  - Lichtenberg, Crispin
T1  - Well‐Defined, Molecular Bismuth Compounds: Catalysts in Photochemically Induced Radical Dehydrocoupling Reactions
JF  - Chemistry – A European Journal
N2  - A series of diorgano(bismuth)chalcogenides, [Bi(di‐aryl)EPh], has been synthesised and fully characterised (E=S, Se, Te). These molecular bismuth complexes have been exploited in homogeneous photochemically‐induced radical catalysis, using the coupling of silanes with TEMPO as a model reaction (TEMPO=(tetramethyl‐piperidin‐1‐yl)‐oxyl). Their catalytic properties are complementary or superior to those of known catalysts for these coupling reactions. Catalytically competent intermediates of the reaction have been identified. Applied analytical techniques include NMR, UV/Vis, and EPR spectroscopy, mass spectrometry, single‐crystal X‐ray diffraction analysis, and (TD)‐DFT calculations.
KW  - bismuth
KW  - chalcogens
KW  - dehydrocoupling
KW  - photocatalysis
KW  - radical reactions
Y1  - 2020
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-224577
VL  - 26
IS  - 64
SP  - 14551
EP  - 14555
ER  - 
TY  - JOUR
A1  - Preitschopf, Tobias
A1  - Sturm, Floriane
A1  - Stroganova, Iuliia
A1  - Lemmens, Alexander K.
A1  - Rijs, Anouk M.
A1  - Fischer, Ingo
T1  - IR/UV Double Resonance Study of the 2‐Phenylallyl Radical and its Pyrolysis Products
JF  - Chemistry – A European Journal
N2  - Isolated 2‐phenylallyl radicals (2‐PA), generated by pyrolysis from a nitrite precursor, have been investigated by IR/UV ion dip spectroscopy using free electron laser radiation. 2‐PA is a resonance‐stabilized radical that is considered to be involved in the formation of polycyclic aromatic hydrocarbons (PAH) in combustion, but also in interstellar space. The radical is identified based on its gas‐phase IR spectrum. Furthermore, a number of bimolecular reaction products are identified, showing that the self‐reaction as well as reactions with unimolecular decomposition products of 2‐PA form several PAH efficiently. Possible mechanisms are discussed and the chemistry of 2‐PA is compared with the one of the related 2‐methylallyl and phenylpropargyl radicals.
KW  - free electron laser
KW  - free jet
KW  - IR spectroscopy
KW  - PAH formation
KW  - radical reactions
Y1  - 2023
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-312338
VL  - 29
IS  - 13
ER  -