Revision of the gas-phase acidity scale below 300 kcal mol(-1).
The gas-phase acidity (GA) scale from (CF(3)CO)(2)NH to (C(2)F(5)SO(2))(2)NH--about a 24 kcal mol(-1) range of gas-phase acidities--was reexamined using the Fourier transform ion cyclotron resonance equilibrium measurement approach. Some additions and modifications to the standard methodology of GA measurements were introduced (estimation of partial pressures from mass spectra of the compounds, instead of the pressure gauge readings and use of long reaction times) to achieve higher reliability. Gas-phase acidities of 18 compounds were determined for the first time. The results reveal a contraction of the previously published values in this part of the scale. In particular, the GA values of (CF(3)SO(2))(2)NH and (C(2)F(5)SO(2))(2)NH (important components of lithium ion battery electrolytes and ionic liquids) were revised toward stronger acidities from 291.8 kcal mol(-1) to 286.5 kcal mol(-1) and from 289.4 kcal mol(-1) to 283.7 kcal mol(-1) (i.e., by 5.3 and 5.7 kcal mol(-1)), respectively. Experimental and computational evidence is presented in support of the current results.
Leito
Ivo
I
Institute of Chemistry, University of Tartu, 2 Jakobi Street, 51014 Tartu, Estonia. ivo.leito@ut.ee
Raamat
Elin
E
Kütt
Agnes
A
Saame
Jaan
J
Kipper
Karin
K
Koppel
Ilmar A
IA
Koppel
Ivar
I
Zhang
Min
M
Mishima
Masaaki
M
Yagupolskii
Lev M
LM
Garlyauskayte
Romute Yu
RY
Filatov
Andrey A
AA