Abstract
A stable El(cb) intermediate, β-cyanoethyl anion (1β), has been synthesized in the gas phase at room temperature under thermal conditions via the fluoride-induced desilylation of 3-(trimethylsilyl)propionitrile. The reactivity and thermodynamic properties of this ion are reported. The cyano group is found to lower the proton affinity of 1β by 29 ± 6 kcal/mol, which represents a particularly large substituent effect. High-level ab initio and density functional calculations have been carried out on 1β and several related species. The computational results are compared to each other, and their accuracy is evaluated.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 4462-4468 |
| Number of pages | 7 |
| Journal | Journal of the American Chemical Society |
| Volume | 118 |
| Issue number | 18 |
| DOIs | |
| State | Published - 1996 |