QUANTUM CHEMICAL MODELING OF Cu2+ ACIDOCHLOROCOMPLEXES CONTAINING ANIONS OF ORGANIC ACIDS
DOI:
https://doi.org/10.15421/jchemtech.v30i1.253575Keywords:
Cu2 complexes, Cl−, anions of organic acids, electronic structure, quantum chemical modelingAbstract
The results of quantum-chemical modeling (Gaussian 09, B3LYP functional) of complex structures that can form from Cu2+ aqua complexes, chloride ions, and anions of organic acids (malonic, succinic, maleic, fumaric, formic, acetic, propionic, butanoic, and acrylic) are considered. It is shown that the series of organic acids under study forms two linear correlation dependences of pK of Cu2+ monosubstituted acidoaquacomplexes on the effective charge of the central atom. One correlation is related to anions of monobasic acids, and the other is related to anions of dibasic acids. Using the parameters of the corresponding pK, z*(Cu2+) dependence and the results of calculation of z*(Cu2+) made it possible to determine the pK value for Cu2+ acrylate complexes, equal to 1.778, information about which is not available in the literature. The degree of change in the effective charge of Cu2+ ions in the [Cu2+(L)] complexes was used to estimate the electron donation power of the ligands: anions of organic acids (−51.95 %) > Cl− (−47.75 %) > H2O (−21.45 %). However, in polyligand aquacomplexes, due to the formation of the bidentate hydrate L · H2O, anions of organic acids are inferior to chloride ions. With the introduction of chlorine anions into the inner coordination sphere of the Cu2+ aqua complexes monosubstituted by organic acid anions, a regular weakening of the Cu2+–L bonds is observed. The degree of decrease in Eb(Cu2+–L) depends on the nature of the organic acid. For saturated structures, ΔEb is in the range of 2–8 kJ/mol; for unsaturated structures, it reaches 20 kJ/mol. The energy of the reaction of substitution of water molecules in Cu2+ acidoaquacomplexes by chlorine anions also changes synchronously (from −4 to −30 kJ/mol).
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