%0 Generic
%A Merrill, Grant N.
%A Dahlke, Gregg D.
%A Kass, Steven R.
%D 1996
%T β-Cyanoethyl Anion: Lusus Naturae
%U https://acs.figshare.com/articles/dataset/_-Cyanoethyl_Anion_Lusus_Naturae/3658719
%R 10.1021/ja953796o.s001
%2 https://acs.figshare.com/ndownloader/files/5748429
%K ab
%K calculation
%K proton
%K Cyanoethyl
%K species
%K desilylation
%K density
%K 1 β
%K reactivity
%K affinity
%K cyanoethyl
%K cyano
%K accuracy
%K Anion
%K initio
%K Naturae
%K ion
%K trimethylsilyl
%K phase
%K substituent
%K anion
%K Lusu
%K E 1 cb
%K kcal
%X A stable E1cb 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.
%I ACS Publications