Refine
Has Fulltext
- yes (13)
Is part of the Bibliography
- yes (13)
Document Type
- Journal article (12)
- Preprint (1)
Language
- English (13) (remove)
Keywords
- bismuth (4)
- cationic species (3)
- aminotroponiminates (2)
- catalysis (2)
- chalcogens (2)
- dehydrocoupling (2)
- electrophilic substitution (2)
- radical reactions (2)
- 1,2-azaborinine (1)
- Bismuth (1)
- Bor (1)
- Boron (1)
- Diborane (1)
- HSAB principle (1)
- Lewis acidity (1)
- Lewis acids (1)
- Metallocene (1)
- Metallocenes (1)
- N-functionalization (1)
- Photoelektronenspektroskopie (1)
- alkali metal (1)
- aminyl radicals (1)
- aromaticity (1)
- bismuth amides (1)
- bond formation (1)
- bonding analysis (1)
- carbon monoxide (1)
- chemistry (1)
- complexes (1)
- crystal structure (1)
- crystallographic analyses (1)
- density functional calculations (1)
- diborenes (1)
- diphosphanes (1)
- heavier pnictogens (1)
- inorganic chemistry (1)
- isomerisation (1)
- ligands (1)
- main-group metals (1)
- methyl exchange (1)
- methylbismuth (1)
- mononuclear (1)
- non-coordinate anionic ligand (1)
- organic and inorganic synthesis (1)
- p-block element (1)
- photocatalysis (1)
- pnictogen coupling (1)
- radical coupling (1)
- radical species (1)
- radicals (1)
- redox chemistry (1)
- redox-active ligands (1)
- salt metathesis (1)
- strained molecules (1)
- tropocoronands (1)
Institute
Sonstige beteiligte Institutionen
Major advances in the chemistry of 5th and 6th row heavy p-block element compounds have recently uncovered intriguing reactivity patterns towards small molecules such as H\(_2\), CO\(_2\), and ethylene. However, well-defined, homogeneous insertion reactions with carbon monoxide, one of the benchmark substrates in this field, have not been reported to date. We demonstrate here, that a cationic bismuth amide undergoes facile insertion of CO into the Bi–N bond under mild conditions. This approach grants direct access to the first cationic bismuth carbamoyl species. Its characterization by NMR, IR, and UV/vis spectroscopy, elemental analysis, single-crystal X-ray analysis, cyclic voltammetry, and DFT calculations revealed intriguing properties, such as a reversible electron transfer at the bismuth center and an absorption feature at 353 nm ascribed to a transition involving σ- and π-type orbitals of the bismuth-carbamoyl functionality. A combined experimental and theoretical approach provided insight into the mechanism of CO insertion. The substrate scope could be extended to isonitriles.
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.
The dimethylbismuth cation: entry into dative Bi-Bi bonding and unconventional methyl exchange
(2021)
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.