Regional
Electrophilic and Nucleophilic Fukui Functions
Efficiently Highlight the Lewis Acidic/Basic Regions in Ionic Liquids
Andrea Cerda-Monje
Rodrigo Ormazábal-Toledo
Carlos Cárdenas
Patricio Fuentealba
Renato Contreras
10.1021/jp5009994.s001
https://acs.figshare.com/articles/journal_contribution/Regional_Electrophilic_and_Nucleophilic_Fukui_Functions_Efficiently_Highlight_the_Lewis_Acidic_Basic_Regions_in_Ionic_Liquids/2309677
The origin of catalysis and selectivity
induced by room temperature
ionic liquids in several organic reactions has putatively been associated
with the concept of <i>cation effect</i> (hydrogen bond
donor ability of the ionic liquids) or <i>anion effect</i> (hydrogen bond accepting ability of the ionic liquids). We show
that there may be cases where this a priori classification may not
be correctly assigned. Cations may concentrate both Lewis acidity
and basicity functions in one fragment of the ionic liquid: an effect
we tentatively call bifunctional distribution of the molecular Lewis
acidity/basicity. Bifunctionality on the cation is however anion dependent
through electronic polarization effects. The molecular distribution
of the Lewis acidity/basicity may simply be assessed by evaluating
the regional Fukui function within a reference ion pair structure.
The model is tested for a set of nine ionic liquids based on the 1-butyl-3-methylimidazolium
cation commonly used as solvent to run organic reactions.
2014-04-03 00:00:00
Ionic LiquidsThe origin
reference ion pair structure
Lewis acidity
hydrogen bond
Regional Electrophilic
Nucleophilic Fukui Functions Efficiently Highlight
polarization effects
cation effect
Fukui function
anion effect
bifunctional distribution
room temperature
hydrogen bond donor ability
basicity functions