@article{HanftRadackiLichtenberg2021, author = {Hanft, Anna and Radacki, Krzysztof and Lichtenberg, Crispin}, title = {Cationic Bismuth Aminotroponiminates: Charge Controls Redox Properties}, series = {Chemistry - A European Journal}, volume = {27}, journal = {Chemistry - A European Journal}, number = {20}, doi = {10.1002/chem.202005186}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-225669}, pages = {6230 -- 6239}, year = {2021}, abstract = {The behavior of the redox-active aminotroponiminate (ATI) ligand in the coordination sphere of bismuth has been investigated in neutral and cationic compounds, [Bi(ATI)\(_{3}\)] and [Bi(ATI)\(_{2}\)L\(_{n}\)][A] (L=neutral ligand; n=0, 1; A=counteranion). Their coordination chemistry in solution and in the solid state has been analyzed through (variable-temperature) NMR spectroscopy, line-shape analysis, and single-crystal X-ray diffraction analyses, and their Lewis acidity has been evaluated by using the Gutmann-Beckett method (and modifications thereof). Cyclic voltammetry, in combination with DFT calculations, indicates that switching between ligand- and metal-centered redox events is possible by altering the charge of the compounds from 0 in neutral species to +1 in cationic compounds. This adds important facets to the rich redox chemistry of ATIs and to the redox chemistry of bismuth compounds, which is, so far, largely unexplored.}, language = {en} } @article{RamlerFantuzziGeistetal.2021, author = {Ramler, Jaqueline and Fantuzzi, Felipe and Geist, Felix and Hanft, Anna and Braunschweig, Holger and Engels, Bernd and Lichtenberg, Crispin}, title = {The dimethylbismuth cation: entry into dative Bi-Bi bonding and unconventional methyl exchange}, series = {Angewandte Chemie International Edition}, volume = {60}, journal = {Angewandte Chemie International Edition}, doi = {10.1002/anie.202109545}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-256543}, pages = {24388-24394}, year = {2021}, abstract = {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.}, language = {en} }