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The solvent effect on the activation free energy of the Finkelstein reaction between methyl iodide and Cl À ions was analysed in terms of the recent Marcus theory unifying the S N 2 and the electron transfer reactions. The homolytic bond dissociation energy and the related resonance energy of interaction of the states seem to be almost solvent independent. The sum of the work term w r and the solvent reorganization energy l 0 /4 depends strongly on the solvent acidity parameter, e.g. E T N , describing the solvation/desolvation of anions. However, after removing the contribution of the specific solvation the linear increase of the remaining part of l 0 /4 with the Pekar factor, describing the non-equilibrium solvent polarization, was observed for six aprotic solvents.

Meso-substituted corroles bearing directly linked ferrocene unit have been synthesized for the first time. Among various methods studied, only the condensation of pentafluorophenyldipyrromethane with a formylferrocene led to this type of product. A triad containing corrole and porphyrin bridged with ferrocene has been obtained by a convergent approach. Bilanes were used as crucial substrates in the porphyrin-forming step. For the first time it was shown that H 2 O-MeOH-HCl conditions are suitable for preparation of various 10-(formylaryl)corroles via the direct condensation of aromatic dialdehydes with dipyrromethanes. Electrochemical studies of 10-ferrocenyl-5,15-bis(pentafluorophenyl)corrole support the possibility of intramolecular electron transfer from the corrole to the ferrocene system after the electrode oxidation of the ferrocene to a ferrocenium cation. We have studied the structure of 1-(corrolyl)-1 0 -(porphyrinyl)ferrocene by 1 H NMR and UV-Vis. NMR spectra show that this compound has more conformational freedom than analogous, previously studied bis-porphyrinylferrocenes. Absorption spectra suggest the lack of strong electronic interaction between ferrocene and porphyrinoids for dyads and significant conjugation for the triad.

Intermolecular interactions between molecules of protic solvents (water, methanol, formic acid, formamide, methylamine and ammonia) and monatomic ions (Li ? , Na ? , K ? , F -, Cl -and Br -) were characterized by the total energy of interaction (E total ) and the amount of charge which is transferred between the solvent molecule and the ion (CT). For the studied systems, linear relationships between E total and ln(CT) were observed and explained. In the case of complexes with metal cations, a good linear correlation between E total and the molar enthalpy of ion solvation (DH o i;solv ), obtained from experimental data for water, methanol, formamide and ammonia, was found. On the other hand, for complexes with anions, a planar regression between E total and two explanatory parameters: DH o i;solv and DH vap (molar heat of vaporization for a given solvent), was established. The latter shows an important role played by solvent-solvent interactions around anions, which is in agreement with some literature predictions based on the mean spherical approximation.