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Molecular Bismuth Cations: Assessment of Soft Lewis Acidity
- Source :
- Chemistry (Weinheim an Der Bergstrasse, Germany)
- Publication Year :
- 2020
-
Abstract
- Three‐coordinate cationic bismuth compounds [Bi(diaryl)(EPMe3)][SbF6] have been isolated and fully characterized (diaryl=[(C6H4)2C2H2]2−, E=S, Se). They represent rare examples of molecular complexes with Bi⋅⋅⋅EPR3 interactions (R=monoanionic substituent). The 31P NMR chemical shift of EPMe3 has been found to be sensitive to the formation of LA⋅⋅⋅EPMe3 Lewis acid/base interactions (LA=Lewis acid). This corresponds to a modification of the Gutmann–Beckett method and reveals information about the hardness/softness of the Lewis acid under investigation. A series of organobismuth compounds, bismuth halides, and cationic bismuth species have been investigated with this approach and compared to traditional group 13 and cationic group 14 Lewis acids. Especially cationic bismuth species have been shown to be potent soft Lewis acids that may prefer Lewis pair formation with a soft (S/Se‐based) rather than a hard (O/N‐based) donor. Analytical techniques applied in this work include (heteronuclear) NMR spectroscopy, single‐crystal X‐ray diffraction analysis, and DFT calculations.<br />Cationic bismuth species [Bi(diaryl)]+ show significant bonding interactions with soft donors EPMe3 (E=S, Se). The 31P NMR chemical shifts of EPMe3 are sensitive to Lewis pair formation and are suggested as an easily accessible experimental parameter for the evaluation of the soft character of a Lewis acid. Using this method, a range of neutral and cationic bismuth species have been investigated and compared to more traditional group 13 and 14 Lewis acids.
- Subjects :
- Substituent
chemistry.chemical_element
010402 general chemistry
01 natural sciences
Catalysis
Bismuth
Base (group theory)
chemistry.chemical_compound
bonding analysis
bismuth
Lewis acids and bases
cationic species
Lewis Acids | Very Important Paper
Electron pair
Full Paper
010405 organic chemistry
Organic Chemistry
Cationic polymerization
General Chemistry
Nuclear magnetic resonance spectroscopy
Full Papers
0104 chemical sciences
Crystallography
Heteronuclear molecule
chemistry
ddc:540
Lewis acids
HSAB principle
Subjects
Details
- Language :
- English
- Database :
- OpenAIRE
- Journal :
- Chemistry (Weinheim an Der Bergstrasse, Germany)
- Accession number :
- edsair.doi.dedup.....86eea42a5fa7f7130ffcbd7e1226ef0b