Ilmar A. Koppel

Equilibrium acidities of superacids.

In this paper, we report the most comprehensive equilibrium superacidity scale that is available to date. Contrary to most of the past works, this scale is set up in a medium of constant composition and the obtained acidity values characterize the acidities of molecules rather than acidities of media. The current scale is thus complementary to the well-known H(0) scale in the information that it provides. The solvent used is 1,2-dichloroethane (DCE). DCE has very weak basic properties (but sufficiently high polarity) and is an appropriate solvent for measuring acidities of very strong acids of diverse chemical nature. DCE acidities of well-known superacids (CF(3)SO(2)OH, (CF(3)SO(2))(2)NH, cyanocarbon acids, etc.) as well as common mineral acids (H(2)SO(4), HI, HBr, etc.) are reported. Acidities of altogether 62 acids have been determined from 176 interlinked relative acidity measurements. The scale spans 15 orders of magnitude (from picric acid to 1,1,2,3,3-pentacyanopropene) and is expected to be a useful tool in design, use, and further acidity measurements of superacidic molecules.

Solute-solvent and solvent-solvent interactions in binary solvent mixtures. 2. Effect of temperature on the ET(30) polarity parameter of dipolar hydrogen bond acceptor-hydrogen bond donor mixtures

The effect of temperature on the Dimroth-Reichardt ET(30) parameter of binary mixtures of dimethyl sulfoxide, acetonitrile and nitromethane with alcohols and water was studied. The ET(30) polarity parameter of many of these binary mixtures exhibits a strong synergism. Dimethyl sulfoxide, acetonitrile and nitromethane form hydrogen-bonded complexes with the alcohols more polar than themselves. The ET(30) values of the mixtures were fitted according to an earlier model, based on solvent exchange equilibria, that allows calculation of the ET(30) values of the hydrogen-bonded complexes. The variation of the ET(30) values of the pure solvents and the hydrogen-bonded complexed solvents with temperature shows that the synergism decreases as the temperature increases.

Solute–solvent and solvent–solvent interactions in binary solvent mixtures. Part 8. The ET(30) polarity of binary mixtures of formamides with hydroxylic solvents

Solvent effects on the binary mixtures of amides with alcohols and water were investigated by means of Reichardts ET(30) solvatochromic indicator. E parameters of binary solvent mixtures of formamide, N-methylformamide and N,N-dimethylformamide with water, methanol, propan-2-ol, 2-methylpropan-2-ol, formamide, N-methylformamide and N,N-dimethylformamide were measured over the whole composition range of the mixtures. Application of a preferential solvation model to the solvatochromic data shows that the preferential solvation of the solvatochromic indicator by the amides decreases in the order N-methylformamide > formamide > N,N-dimethylformamide. Synergism is observed for the mixtures of the amides with alcohols of similar polarity (E value), i.e. methanol–formamide, methanol–N-methylformamide, propan-2-ol–N,N-dimethylformamide and 2-methylpropan-2-ol–N,N-dimethylformamide binary systems. Copyright

Critical test of performance of B3LYP functional for prediction of gas-phase acidities and basicities

Abstract The gas-phase acidities and basicities for 49 acids and 32 bases, calculated using B3LYP hybrid DFT method and 6-31G ∗ , 6-31+G ∗ , 6-311+G ∗∗ , and 6-311+G(3df,3pd) basis sets are compared with corresponding experimental values. The best results were obtained with 6-311+G(3df,3pd) basis set; the average absolute errors were below 2.5 kcal/mol both for basicities and acidities. Good results for both acidities and basicities (the average absolute errors were ⩽3 kcal/mol) were also obtained using the 6-311+G ∗∗ basis set and even with a moderate 6-31+G ∗ basis set (mean absolute errors were

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.

IEF-PCM Calculations of Absolute pKa for Substituted Phenols in Dimethyl Sulfoxide and Acetonitrile Solutions

Absolute (nonrelative) pKa calculations for substituted phenols were carried out in nonaqueous media, demonstrating the predictive power of the integral equation formalism PCM method with a mean unsigned error of 0.6 pKa units for DMSO and 0.7 pKa units for MeCN at the B3LYP/6-31+G** level of theory combined with the scaled B3LYP/6-311+G** gas-phase data. At the same time, the correlation between the calculated and experimental pKa values yielded the value of the linear regression slope very close to unity for both DMSO and MeCN. Computation of pKa of neutral acids in nonaqueous solutions with a reasonable precision obviously depends on carefully tuned cavities, optimized for nonaqueous solutions. The ability of continuum solvation model to compensate charge escape from the cavity, which is prominent in the case of anions, is also required. And finally, good quality gas-phase data is essential to achieve required pKa precision.

Acidity of Strong Acids in Water and Dimethyl Sulfoxide

Careful analysis and comparison of the available acidity data of HCl, HBr, HI, HClO4, and CF3SO3H in water, dimethyl sulfoxide (DMSO), and gas-phase has been carried out. The data include experimental and computational pKa and gas-phase acidity data from the literature, as well as high-level computations using different approaches (including the W1 theory) carried out in this work. As a result of the analysis, for every acid in every medium, a recommended acidity value is presented. In some cases, the currently accepted pKa values were revised by more than 10 orders of magnitude.

SUPERACIDITY OF NEUTRAL BRONSTED ACIDS IN GAS PHASE

Quantum chemical calculations of potentially superacidic neutral Brönsted acids were carried out using the PM3 method. It was shown that the PM3 method can be used to predict the gas phase acidities of acidic compounds only if empirical corrections are made. A strong acidifying effect is predicted for a new family of compounds in which an sp2 oxygen is substituted by an (DOUBLE BOND) NSO2CF3 group. So, for example, such replacement is expected to result in acid strengthening by 47.5 kcal/mol in the case of CH3CHO and by 22.7 kcal/mol in the case of CF3SO2OH. The acidities of such compounds are predicted to be increased further (nonadditively) by stepwise replacements of (DOUBLE BOND) O by (DOUBLE BOND) NSO2CF3. The geometries of known superacidic systems were reproduced quite well by PM3 method. The geometries of several superacidic systems were analyzed.

Basicity Limits of Neutral Organic Superbases

The potential limits of superbasicity achievable with different families of neutral bases by expanding the molecular framework are explored using DFT computations. A number of different core structures of non-ionic organosuperbases are considered (such as phosphazenes, guanidinophosphazenes, guanidino phosphorus ylides). A simple model for describing the dependence of basicity on the extent of the molecular framework is proposed, validated, and used for quantitatively predicting the ultimate basicities of different compound families and the rates of substituent effect saturation. Some of the considered bases (guanidino phosphorus carbenes) are expected to reach gas-phase basicity around 370 kcal mol(-1), thus being the most basic neutral bases ever reported. Also, the classical substituted alkylphosphazenes were predicted to reach pK(a) values of around 50 in acetonitrile, which is significantly higher than previously expected.

The immense acidifying effect of the supersubstituent NSO2CF3 on the acidity of amides and amidines of benzoic acids in acetonitrile

The pKa values of acidic dissociation of the conjugate acids of derivatives of benzoate anions, where one or two oxygen atoms are replaced by an NSO2CF3 group, N-aroyltrifluoromethanesulfonamides 1a–f and previously unreported N,N′-bis(trifluoromethylsulfonyl)benzamidines 4a–f, were measured in acetonitrile. In the case of the parent compound, the incorporation of the first NSO2CF3 group instead of the oxygen atom leads to a sharp (by 9.6 pKa units) increase in the acidity, whereas the replacement of the second oxygen atom results in a further huge increase in the acidity by 4.9 powers of ten. It was found that the sensitivity of the reaction series under consideration towards substituent effects (in the benzene ring) decreases in the following order: benzoic acids > benzamides (1a–f) > benzamidines (4a–f). The results of this work carry potentially important implications for the design of new types of superacids and catalytic materials.