A DFT study of fulvic acid binding with bivalent metals: Cd, Cu, Mg, Ni, Pb, Zn

3,7,8-Trihydroxy-3-methyl-10-oxo-4,10-dihydro-1H,3H-pyrano [4,3-b]chromene-9-carboxylic acid is a structurally well-characterized fulvic acid (FA) capable to act as a polyfunctional bidentate ligand in the complexes with metal ions. Investigations of the formation mechanisms and structure of the abovementioned FA complexes with bivalent metals [Cd(II), Cu(II), Mg(II), Ni(II), Pb(II) and Zn(II)] are presently an actual and trending topic in the modern chemistry of humic and fulvic acids. Furthermore, the importance of the theoretical DFT investigations of binding of metals with fulvic acids is stipulated by the lack of the relevant experimental structural data for such complexes. The quantum chemical calculations have shown that, of the four possible FA tautomers, the two FA forms are more stable. The wavefunction analysis and computed reactivity descriptors (electrostatic potential, Hirshfeld surface analysis, natural population analysis charges, and condensed Fukui indexes) give the insight on the properties and reactive ability of these two different forms of the FA. The computed thermochemical parameters of the ion-exchange reaction explain the metal binding affinity and selectivity of the FA forms. (c) 2020 Elsevier Inc. All rights reserved.

Automated summary

The compound 3,7,8-Trihydroxy-3-methyl-10-oxo-4,10-dihydro-1H,3H-pyrano [4,3-b]chromene-9-carboxylic acid is a well-characterized fulvic acid that acts as a polyfunctional bidentate ligand in complexes with metal ions. The study of the formation mechanisms and structure of the FA complexes with bivalent metals is a trending topic in modern chemistry, and theoretical DFT investigations are important due to the lack of experimental structural data. Computational analysis reveals the stability of two out of four possible FA tautomers and provides insight into their properties and reactive ability.