Solvation of Ferrocene, Cobaltocene, and Their Ions
by the Data of Quantum-Chemical Calculations¹

An. M. Kuznetsov^a,z, A. N. Maslii^a, and L. I. Krishtalik^b

^a Kazan State Technological University, ul. K. Marksa 68, Kazan, 420015 Russia

^b Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences,
Leninskii pr. 31, Moscow, 119991 Russia

Received November 8, 2007

Abstract—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 dimethyl-
sulfoxide 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.

Key words: ferrocene, cobaltocene, dimethylsulfoxide, B3LYP method, solvation, PCM model, redox pro-
cesses, electrode potentials, transfer energy

DOI: 10.1134/S1023193509010121

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