The formation constants, K-s for 1:1 complexes of the cis-syn-cis and cis-anti-cis isomers of dicyclohexyl-18-crown-6 with sodium and potassium cations have been electrochemically determined in 10 nonaqueous (protic and aprotic) media. Linear correlations were obtained for log K-s with standard Gibbs transfer energies of the cation from water to a given solvent. The cis-anti-cis isomer was found to be a weaker complexer than the cis-syn-cis one and this was elucidated in terms of the ligand solvation. Energy-minimized structures of the ligands and complexes suuuounded by methanol and acetonitrile molecules were established by molecular dynamics computations.
The effect of carboxylic acids of different strenght on polarographic behaviour of p-chloronitrobenzene in N, N-dimethylformamide has been investigated. In the presence of each acid a pre-wave appeared at a more positive potential than the original one, which was associated with the cathodic reduction of a hydrogen-bonded adduct, formed between the nitrocompound and the acid molecules in the double layer of the electrode. A linear correlation has been found between delta E-1/2 and pK(DMF/HA) (pK(DMF/HA) refers to the value of the pK-a measured in N, N-dimethylformamide, whereas delta E-1/2=E(pre-wave/1/2) - E(original wave/1/2)). Measurements in a solvent series in the presence of benzoic acid (BA) led to the correlation between delta E-1/2 and pK-BA (the symbol pK-BA denotes the value measured in a given solvent). The slopes of regression lines are discussed in terms of the double layer effect on the basicity of the -NO2 group.