The electrochemical behaviour of a series of Fischer ethoxycarbene complexes of the type [(CO)(5)Cr=C(OEt)R] with R=2-thienyl (1), 2-furyl (2), 2-(N-methylpyrrolyl) (3), N-methyl-2-(2'-thienyl)pyrrole) (4) and 2,2'-thienylfuran (5), is investigated by means of cyclic voltammetry. Results show that the first one electron reduction process is sensitive to the energy, shape and distribution of the LUMO orbital, leading to a linear relationship between the formal reduction potential and the LUMO energy: E-0'(C-carbene)= -0.70 E-LUMO-3.44 (R-2 = 1.00) which is valid over a large potential range. The dimeric heteroarene substituents of 4 and 5 lead to enhanced stabilization of the reduced complexes 4 and 5, making another one electron reduction possible. The formal reduction potential, E-0'(Cr) of the first oxidation process of 1-5 lays within a narrow potential range of 0.43-0.50 V vs. Fc/Fc(+), is Cr-based and is mainly sensitive to the electrophilic character of the heteroarene ring directly attached to the carbene carbon. (C) 2013 Elsevier Ltd. All rights reserved.