Solvation of ferrocene, cobaltocene, and their ions by the data of quantum-chemical calculations

Quantum-chemical calculations of solvation energy for ferrocene and cobaltocene molecules and their ionic forms in water, acetonitrile, methanol, acetone, and dimethylsulfoxide are performed in terms of the density functional method of the B3LYP type, taking into account the effect of solvent and using the Polarized Continuum Model (PCM). It is shown that the optimization of metallocene structure in liquid introduces only slight quantitative changes as compared with the data calculated for the structures optimized in the gas phase. It is shown that earlier observed deviation of experimental redox potentials of cobaltocene system in dimethylsulfoxide from the regularities of continuum electrostatics is caused by a stronger effect of this solvent on the distribution of electron density over the molecule of dissolved substance.