Electrochemistry of Fischer alkoxycarbene complexes of chromium : the use of Density Functional Theory to predict and understand oxidation and reduction potentials
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Authors
Landman, Marile
Lui, Renyuan
Van Rooyen, Petrus H.
Conradie, Jeanet
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Publisher
Elsevier
Abstract
The 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.
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Keywords
Fischer alkoxycarbene Cr-complexes, DFT calculations
Sustainable Development Goals
Citation
Landman, 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.