Collect. Czech. Chem. Commun. 1980, 45, 360-368

Association of radical anions alkali metal cations. III. Experimental and theoretical study of the associates of nitrobenzene radical anions with Li+, Na+, K+, Cs+ and (n-C4H9)4N+ cations

Stanislav Miertuš, Ondrej Kyseľ and Juraj Danciger

Polymer Institute, Slovak Academy of Sciences, 809 34 Bratislava


The nitrobenzene radical anion prepared by electrolysis was studied by UV spectroscopy. Formation of associates with Li+, Na+, K+, Cs+ and n(C4H9)4N+ cations was examined. It has been found that associates are also formed in a polar medium such as dimethylformamide. The enthalpy of the associated-free ion equilibrium was estimated as being equal to 6+4 kJ/mol-1. The quantum-chemical LHP method (in the π-approximation) was employed to study a simple ion pair model used for calculation of the most stable geometrical structure.