In this work the electrochemical behavior, of three Fe(II) polypyridinc complexes [Fe(bipy)(3)](2+), [Fe (phen)(3)](2+), and [Fe(terpy)(2)](2+) in acetonitrile solution was explored, to understand the mechanism of the molecular catalysis of carbon dioxide reduction, for metal complexes with no available coordination sites and inert to substitution. Cyclic voltammetry experiments using as working electrodes glassy carbon and platinum in the presence and in the absence of CO2 were carried out. All the compounds present the oxidation Fe(II)L-n + e reversible arrow Fe(III)L-n. For the tris chelate systems [Fe(phen)(3)](2+) and [Fe(bipy)(3)](2+), three reduction processes over the coordinated ligands are observed. On the other hand, the bis chelate complex [Fe(terpy)(2)](2+) shows two reductions processes center in ligands. For experiments with a glassy carbon electrode, a third reduction process that yield the species [Fe-0(terpy-)(2)] is detected. DFT calculations support the idea for the electrochemical reduction in the coordinated ligands. For compound [Fe(bipy)(3)](2+), the catalytic rate constant (k) and the turnover frequency (TOF) relationships were calculated. Spectroelectrochemical experiments in the absence and in the presence of CO2 were also carried out, demonstrating the regeneration of catalysts. An outer sphere homogenous electron transfer mechanism between the catalyst and CO2 is proposed, where high negative redox potential values favored the molecular catalysis. (C) 2017 Elsevier Ltd. All rights reserved.