TY  - JOUR
A1  - Ramler, Jaqueline
A1  - Fantuzzi, Felipe
A1  - Geist, Felix
A1  - Hanft, Anna
A1  - Braunschweig, Holger
A1  - Engels, Bernd
A1  - Lichtenberg, Crispin
T1  - The dimethylbismuth cation: entry into dative Bi-Bi bonding and unconventional methyl exchange
JF  - Angewandte Chemie International Edition
N2  - The dimethyl bismuth cation, [BiMe\(_2\)(SbF\(_6\))], has been isolated and characterized. Reaction with BiMe\(_3\) allows access to the first compound featuring Bi→Bi donor–acceptor bonding. In solution, dynamic behavior with methyl exchange via an unusual S\(_E\)2 mechanism is observed, underlining the unique properties of bismuth species as soft Lewis acids with the ability to undergo reversible Bi−C bond cleavage.
KW  - inorganic chemistry
KW  - methyl exchange
KW  - bismuth
KW  - cationic species
KW  - electrophilic substitution
KW  - Lewis acidity
Y1  - 2021
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-256543
VL  - 60
ER  - 
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  -