Resumo

VON ESCHWEGE, Karel G.  e  CONRADIE, Jeanet. Redox potentials of ligands and complexes - a DFT approach. S.Afr.j.chem. (Online) [online]. 2011, vol.64, pp.203-209. ISSN 1996-840X.

A review of the limited literature concerned with theoretical ways to predict experimentally measured redox potentials of ligands and complexes is presented. Electrochemical and related DFT studies involving series of para-substituted nitrobenzenes and β-diketone bidentate ligands are discussed. New studies involving ferrocenes and bimetallic complexes (containing both rhodium and iron) are additionally reported. Correlations of redox potentials with calculated descriptors; electron affinity (EA), group electronegativity (x_R), electrophilicity index (ω), LUMO energy (E_LUMO) and HOMO energy (E_HOMO) - obtained from calculated electronic energies of neutral, anionic and cationic molecules, are compared. Observed E⁰,E_pa or E_pc gave excellent correlations in the linear relationships between E_pc and E_LUMO (R² > 0.99), and E_pa and E_HOMO (R² > 0.92). Close correlation with the HOMO-1 energy was also found with the ferrocene-based second oxidation in the Rh complex.

Palavras-chave : Oxidation; reduction; predict; electron affinity; electrophilicity index; electronegativity; LUMO energy; HOMO energy.

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