Publication | Open Access
Bismuth Cations: Fluoride Ion Abstraction, Isocyanide Coordination, and Impact of Steric Bulk on Lewis Acidity
19
Citations
61
References
2023
Year
The molecular compound [BiDipp<sub>2</sub> (SbF<sub>6</sub> )], containing the bulky, donor-free bismuth cation [BiDipp<sub>2</sub> ]<sup>+</sup> has been synthesized and fully characterized (Dipp=2,6-iPr<sub>2</sub> -C<sub>6</sub> H<sub>3</sub> ). Using its methyl analog [BiMe<sub>2</sub> (SbF<sub>6</sub> )] as a second reference point, the impact of steric bulk on bismuth-based Lewis acidity was investigated in a combined experimental (Gutmann-Beckett and modified Gutmann-Beckett methods) and theoretical approach (DFT calculations). Reactivity studies of the bismuth cations towards [PF<sub>6</sub> ]<sup>-</sup> and neutral Lewis bases such as isocyanides C≡NR' revealed facile fluoride ion abstraction and straightforward Lewis pair formation, respectively. The first examples of compounds featuring bismuth-bound isocyanides have been isolated and fully characterized.
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