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The hydrophobic properties of [15]crown‐5 enable the formation of inner sphere complexes with ClO−4 as a ligand in inert solvents such as CH3NO2. Conductivity and NMR measurements reveal the existence of M(II)([15]crown‐5)(ClO4)2 and [M(II)([15]crown‐5)(ClO4)]+ (M(II) = Co, Mg, Zn, Ca) in solution. The unusually slow methanol exchange rate between [M(II)([15]crown‐5)(CH3OH)2]++ (M(II) = Co, Mg, Zn) and bulk solvent can be explained by the cavity diameter of the macrocyclic ligand applying a donor acceptor model.

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Specific and statistical solvation of Co(II)‐ions in mixtures of methanol with dimethylformamide respectively hexamethylphosphoric triamide was found by 1H‐NMR‐spectroscopy. Relations are given, which correlate these possible solvation models with the kinetics of solvent exchange. On this basis, specific outersphere solvation of the methanol rich Co(II)‐solvate‐complexes by dimethylformamide can be deduced. For mixtures of hexamethylphosphoric triamide with methanol, the statistical solvation behaviour is additionally favoured by a strong solvent‐solvent interaction.