Landman, MarileLui, RenyuanVan Rooyen, Petrus H.Conradie, Jeanet2014-02-042014-02-042013-12Landman, M, Liu, R, Van Rooyen, PH & Conradie, J 2013, 'Electrochemistry of Fischer alkoxycarbene complexes of chromium : the use of Density Functional Theory to predict and understand oxidation and reduction potentials', Electrochimica Acta, vol. 114, pp. 205-214.0013-4686 (print)1873-3859 (online)10.1016/j.electacta.2013.10.013http://hdl.handle.net/2263/33279The electrochemical behaviour of a series of Fischer ethoxycarbene complexes of the type [(CO)5Crdouble bond; length as m-dashC(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: E0′(Ccarbene) = –0.70 ELUMO–3.44 (R2 = 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, E0′(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.en© 2013 Elsevier. All rights reserved. Notice : this is the author’s version of a work that was accepted for publication in Electrochimica Acta. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published in Electrochimica Acta, vol.114, pp.205-214, 2013. doi : 10.1016/j.electacta.2013.10.013Fischer alkoxycarbene Cr-complexesDFT calculationsReduction (Chemistry)ElectrochemistryChromium compoundsChromium compounds -- OxidationDensity functionalsPostprint Article