β-Cyanoethyl Anion: Lusus Naturae
Grant N. Merrill
Gregg D. Dahlke
Steven R. Kass
10.1021/ja953796o.s001
https://acs.figshare.com/articles/dataset/_-Cyanoethyl_Anion_Lusus_Naturae/3658719
A stable E1<sub>cb</sub> intermediate, β-cyanoethyl anion
(<b>1</b>β), 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 <b>1</b>β 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
<b>1</b>β and several related species. The computational
results
are compared to each other, and their accuracy is
evaluated.
1996-05-08 00:00:00
ab
calculation
proton
Cyanoethyl
species
desilylation
density
1 β
reactivity
affinity
cyanoethyl
cyano
accuracy
Anion
initio
Naturae
ion
trimethylsilyl
phase
substituent
anion
Lusu
E 1 cb
kcal